Review

Cite This: Chem. Rev. 2019, 119, 8781−8845 pubs.acs.org/CR

Chemical Bonding and Bonding Models of Main-Group Compounds

Lili Zhao,† Sudip Pan,† Nicole Holzmann,‡ Peter Schwerdtfeger,*,§ and Gernot Frenking*,†,∥,⊥
†
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center
for Advanced Materials, Nanjing Tech University, Nanjing 211816, China
‡
Scientific Computing Department, STFC Rutherford Appleton Laboratory, Harwell Oxford, Didcot OX11 0QX, United Kingdom
§
The New Zealand Institute for Advanced Study, Massey University (Albany), 0632 Auckland, New Zealand
∥
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, D-35043 Marburg, Germany
⊥
Donostia International Physics Center (DIPC), P.K. 1072, 20080 Donostia, Euskadi, Spain
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ABSTRACT: The focus of this review is the presentation of the most important aspects
of chemical bonding in molecules of the main group atoms according to the current state
of knowledge. Special attention is given to the difference between the physical
mechanism of covalent bond formation and its description with chemical bonding
models, which are often confused. This is partly due to historical reasons, since until the
development of quantum theory there was no physical basis for understanding the
chemical bond. In the absence of such a basis, chemists developed heuristic models that
proved extremely valuable for understanding and predicting experimental studies. The
great success of these simple models and the associated rules led to the fact that the
model conceptions were regarded as real images of physical reality. The complicated
world of quantum theory, which eludes human imagination, made it difficult to link
heuristic models of chemical bonding with quantum chemical knowledge. In the early
days of quantum chemistry, some suggestions were made which have since proved untenable. In recent decades, there has been
a stormy development of quantum chemical methods, which are not limited to the quantitative accuracy of the calculated
properties. Also, methods have been developed where the experimentally developed models can be quantitatively expressed and
visually represented using mathematically well-defined terms that are derived from quantum chemical calculations. The
calculated numbers may however not be measurable values. Nevertheless, as orientation data for the interpretation and
classification of experimental findings as well as a guideline for new experiments, they form a coordinate system that defines the
multidimensional world of chemistry, which corresponds to the Hilbert space formalism of physics. The nonmeasurability of
model values is not a weakness of chemistry but a characteristic by which the infinite complexity of the material world becomes
scientifically accessible and very useful for chemical research. This review examines the basis of the commonly used quantum
chemical methods for calculating molecules and for analyzing their electronic structure. The bonding situation in selected
representative molecules of main-group atoms is discussed. The results are compared with textbook knowledge of common
chemistry.

CONTENTS 6. Physical Reality and Chemical Bonding Models 8794

7. Selected Examples of Chemical Bonds in Main-
1. Introduction 8782 Group Compounds 8795
2. The Physical Nature of the Chemical Bond 8783 7.1. H2+, H2, Li2+, Li2 8795
3. Historical Development and Present Situation of 7.2. H2, N2, CO, and BF 8797
Bonding Models for Main-Group Compounds: 7.3. First Octal-Row Sweep Li2−F2 and Related
The Lewis Paradigm 8786 Molecules 8799
4. Quantum Chemical Methods for Calculating 7.3.1. Li2, Be2 and Related Molecules 8801
Molecular Structures and Properties 8787 7.3.2. B2 and Related Molecules 8801
4.1. Molecular Orbital (MO) Theory 8788 7.3.3. C2 and Related Molecules 8803
4.2. Density Functional Theory (DFT) 8789 7.3.4. N2 and Related Molecules 8806
4.3. Valence-Bond (VB) Theory 8790 7.3.5. O2, F2 and Related Molecules 8808
5. Quantum Chemical Methods for Analyzing the 7.4. Chemical Bonding in Heavier Main-Group
Chemical Bond in Molecules 8790 Compounds 8810
5.1. Natural Bond Orbital Method (NBO) 8790
5.2. Quantum Theory of Atoms in Molecules
(QTAIM) 8791 Special Issue: Frontiers in Main Group Chemistry
5.3. Energy Decomposition Analysis and Natural Received: December 2, 2018
Orbitals for Chemical Valence (EDA-NOCV) 8792 Published: June 28, 2019

© 2019 American Chemical Society 8781 DOI: 10.1021/acs.chemrev.8b00722

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Chemical Reviews
7.4.1. Hypervalent Molecules: Valence, Orbital
Symmetry, and 3-Center, 4-Electron
Bonding 8811
7.4.2. Hypervalent Molecules: SF6 and PF5 8812
7.4.3. Multiple Bonds of Heavy Diatomic
Molecules Na2−Cl2 and N2−Bi2 and
Related Molecules 8813
7.4.4. Multiple Bonds of Heavy Main-Group
Atoms: N2/N4 vs P2/P4 8815
7.4.5. Multiple Bonds of Heavy Main-Group
Atoms: X2CCX2 vs X2EEX2 (E = Si − Pb; X =
H, F) 8817
7.4.6. Multiple Bonds of Heavy Main-Group
Atoms: HCCH vs HEEH (E = Si − Pb) 8819
8. Dative Bonding in Main-Group Compounds 8822
9. The Octet Rule and the Atomic Valence Space of
Main-Group Atoms 8827
10. Relativistic Effects in Main-Group Compounds 8829
11. Concluding Remarks 8834
Author Information 8835
Corresponding Authors 8835
ORCID 8835
Notes 8835
Biographies 8835
Acknowledgments 8835
References 8835
1. INTRODUCTION
In the year 2000, one of the present authors wrote a review for
the centennial issue of this journal entitled “The Nature of the
Bonding in Transition-Metal Compounds”.1 The introduction
describes the peculiar dichotomy of using heuristic bonding
models along with quantum chemical calculations for the
description of molecular structures, which is characteristic for
present-day chemical research. This situation holds even more
for main-group compounds, where the depiction of the bonding
situation in terms of “resonating” Lewis structures and molecular
orbitals (MOs) in combination with quantum chemical
calculations along with charge- and energy-partitioning methods
is frequently presented side-by-side. The connection between
the experimental observations and numerical results of such
calculations is usually guided by the attempt to grasp the
complicate numerical information, which is provided by
quantum chemical calculations, with a simple bonding model.
This can clearly be considered a Hercules (and sometimes
Sisyphus) task, which tries to connect two extremes: The
quantum theoretical description of the electronic structure,
which is governed by the Schrö dinger equation in the
nonrelativistic case and the Dirac equation in the relativistic
case, is given in mathematical terms that are elusive objects for
the human imagination trained with classical objects. It is a
genuine chemical approach to illustrate this with symbols and
figures that are as simple as possible, appealing, and useful to
chemists.
The most important model for chemical bonding is clearly the
heuristic assignment of an electron pair to a chemical bond first
suggested by Gilbert Lewis in 1916.2 It was developed by
inspection of chemical structures and stabilities and by
evaluating similarities mainly of main-group compounds of the
first octal row of the periodic system. The model was further
elaborated by Langmuir in 1919−1921,3−6 who introduced the
octet rule7 along with the 18- and 32-electron rules and coined
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the term “covalent bonding” at a time when modern quantum
theory was not developed yet. Over the course of time it was
modified and refined like a neural network, using the increase of
experimental observations as feedstock for improvement.
The electron-pair model of a covalent bond may be
considered as a stroke of genius, where the yet unknown
quantum chemical nature of the chemical bond is miraculously
converted to and hidden in a very simple representation. It is
unsurpassed in its convenience to depict and represent
molecular structures and reactivities. The model has been
somewhat modified over the years and the rules for using Lewis
structures slightly changed in the course of time, but the
essential features remain the same until today. This is
astonishing, because the origin of covalent bonding is a quantum
theoretical effect. This was shown for the first time by Heitler
and London in 1927,8 when they analyzed the chemical bond in
H2 using the newly developed quantum theory by Heisenberg9
and Schrödinger.10 Linus Pauling was the first who presented a
bridge between the heuristic electron-pair bonding model of
Lewis and quantum theory in his epochal book “The Nature of
the Chemical Bond”, which quickly became the reference
standard in the community for describing chemical bonding.11
This was done at a time when powerful computers were not yet
available and quantum chemistry was in its infant stage. Later
studies showed that the nature of the chemical bond is far more
complicated than initially thought and that the connection
between the Lewis model and the physical nature of chemical
bonding is quite intricate. This does not come as a surprise.
Considering the enormous complexity of the physical universe
and the rather small numbers of chemical elements and
particles12 from which it is constructed, it requires a sheer
infinite variety of chemical bonding to create such a richness of
the material phenomena in our universe including the complex
biochemical nature of animate beings.
A fundamental approach of chemistry deals with the
classification and arrangement of the molecular structures and
reactivities using simple models, rules, and guidelines, which
serve as classification schemes for the vast amount of
compounds and reactions. Chemistry as it is currently applied
and understood can be considered as the science of fuzzy
concepts, because many models are poorly defined and
somewhat arbitrarily used and, yet, they have proven to be
very helpful as an orientation for experimental studies. Chemical
models were termed as “unicorns”,13 because every chemist
seems to know what they mean although a precise definition is
often not available. For a scientist who is trained with exact
physical quantities, chemical models may appear as unscientific
chimera. But if we only would focus on measurable quantities
(so-called observables in quantum mechanical terms), dis-
regarding the many beautiful concepts developed over the past
centuries, chemistry would be deprived of its inner beauty and
many major discoveries would not have been made. The term
“chemical bond” is not an observable in a strict quantum
mechanical sense but refers to the extensive symbolism used in
chemistry to represent the attractive force between atoms or
molecules. A puristic viewpoint ignores their enormous
usefulness for breaking down the ever increasing complexity
and richness of chemical findings into well-ordered classification
schemes. Chemical bonding models are not right or wrong, they are
more or less usef ul. The usefulness of models comes from their
help as an ordering scheme of experimental observations and
their use as guidance for future experiments and interpretations.
But it is a grave mistake to confuse a bonding model with the
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physical nature of the interatomic interactions that give rise to
what we call a chemical bond. This has been the source of
numerous controversies and misunderstandings in the past.
This review article has two goals. One goal is to present the
current understanding of the physical nature of covalent
bonding in main-group compounds. This shall be done without
digging deeply into the mathematical details of the quantum
chemical description of the interatomic interactions. This is not
an easy task, because the quantum theoretical description of the
chemical bond is quite complicated and has many facets, which
cannot all be accounted for in the present review article. We
strive for a concise presentation of the most important results
and conclusions that came out of the numerous studies, which
were done since the ground-breaking work by Heitler and
London. For a more detailed discussion of the quantum
theoretical nature of the chemical bond, we refer to pertinent
review articles and monographs.14−16
The second goal of this account concerns the use of modern
chemical bonding models and the Lewis electron-pair
approximation for describing molecular structures and reac-
tivities. The central aspect of this work aims at bridging bonding
models with the quantum theoretical nature of the chemical
bond. The focus is the connection between the results of
standard quantum chemical calculations, which are mostly based
on molecular orbital (MO) theory or density functional theory
(DFT), and the presentation of molecules with a bonding
model. There are various methods available that convert the
results of theoretical calculations into models that aim at
describing the essential chemical features of the investigated
species. The most important methods will be critically discussed,
and the results for archetypical molecules will be presented. It is
not possible to review all kinds of chemical bonds of main-group
compounds in this work. The present account is restricted to
selected classes of archetypical molecules and bonds, which
represent not all but the most important types of chemical bonds
in molecules of the sp-block elements of the periodic table.
2. THE PHYSICAL NATURE OF THE CHEMICAL BOND
The physical origin of the covalent bond was for a long time a
mystery not only for chemists but for science in general. It was
clear that from the four elementary forces in physics only
electrostatic forces could account for the strong interatomic
interactions that yield a chemical bond. But the attraction takes
place between neutral species, and the application of the classical
Coulomb law does not give results that agree with experimental
findings. Gilbert Lewis knew about the problem when he
suggested in 1916 that the chemical bond should be identified
with an electron pair. He speculated, “Electric forces between
particles which are very close together do not obey the simple law of
inverse squares which holds at greater distances”.2 When the puzzle
about the physical origin of the chemical bond was finally solved
by Heitler and London in 1927,8 who employed the newly
developed quantum theory by Heisenberg9 and Schrödinger10
to the interactions between two hydrogen atoms as well as
between two helium atoms, it came as a shock not only to
chemists but to natural sciences altogether. The solution was in
conflict with all ideas that had been envisaged by scientists for
explaining the chemical bond.
According to the quantum theoretical approach by Heitler
and London, the electrostatic interactions between atoms have
to be described in terms of mathematical functions describing
quantum objects rather than classical particles. Chemical
bonding comes from the interference of spatially extended
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wave functions, which may either have a positive (+) or a
negative (−) sign. The alternative signs yield two possible
options for the new wave function, which describe the bonding
and antibonding combinations of the interacting electrons. The
positive interference leads to an accumulation of electronic
charge in the interatomic region whereas the negative
interference induces charge depletion. It is only at the level of
the wave function that the information, which is provided by the
leading sign, becomes operative. The electronic charge is derived
from squaring the wave function, which annihilates the sign
information given by the wave function. Mulliken,17 Hund,18
Lennard-Jones,19 and Hü ckel20 recognized the gain in
information that is provided by the sign of the wave functions.
Many years later Fukui21 developed the frontier molecular
orbital (FMO) theory and Woodward and Hoffmann22
introduced the orbital symmetry rules for pericyclic reactions,
which are based on the information that is provided by the
orbitals. Nevertheless, chemists still have difficulties in accepting
the more fundamental nature of the wave function as the origin
of the chemical bond compared to a simple particle character of
the electrons.
The most important conclusion that stems from the Heitler−
London work is the finding that the physical origin of the
covalent bond is not due to the formation of an electron pair.
Covalent bonding comes from the interference of the wave
functions of the interacting species.23 Chemical bonding occurs
already when only one electron occupies the new wave function,
such as in H2+. The second electron usually strengthens the
chemical bond further such as in H2, but there are molecules
where the second electron even weakens the bond. This is the
case in Li2, which has lower bond dissociation energy than
Li2+.24 The frequent occurrence of molecules with an even
number of electrons is due to the Pauli principle, which allows a
maximum of two electrons occupying the same spatial orbital.
This is a quantum theoretical postulate originating from the
more fundamental spin statistics theorem, which requests that
electrons are different by at least one quantum number, but it is
not the physical origin per se of the chemical bond. The finding
that electron pairing is not the physical origin of the chemical
bond becomes obvious by the stability of numerous molecules,
which have unpaired electrons such as dioxygen O2 and the large
number of paramagnetic transition metal complexes. The
specific e−e pairing interaction is repulsive in most cases, and
it can be energetically more favorable that the two electrons
occupy spatially different orbitals, as for example in the ground
state of O2. The stabilization of the second electron in a doubly
occupied MO stems mainly from the interference of the wave
function.
We wish to emphasize that Pauli repulsion does not introduce
a new type of physical force, which may be overcome by other
forces. All interatomic forces, which are relevant for chemical
bonding, come from Coulombic interactions. However, the
mathematical description of Coulomb forces between atoms
requires quantum theoretical postulates. The Pauli (exchange)
forces are due to the requirement that the wave function must be
antisymmetric, which requests that two electron may not have
the same quantum numbers.
The large difference between the classical and the quantum
theoretical description of an electron comes to the fore when
calculating the electron−electron repulsion as a function of the
e−e distance either way. Figure 1 shows the 1/r12 curve for the
repulsion between two point charges q calculated following the
Coulomb law for classical particles (eq 1) and the repulsion
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Chemical Reviews
Figure 1. Calculated interaction energies between two charged particles
as a function of their distance r12. Repulsive interactions between two
electrons calculated classically ΔEelstat(classical) = q1q2/r12 (dashed
line); quasiclassical repulsion between two electrons in 1s orbitals
ΔEelstat = ∫ ρ1ρ2/r12 dτ1 dτ2 (dotted line); exchange repulsion between
two electrons with the same spin in 1s orbitals ΔEPauli (solid line).
Reprinted with permission from ref 28. Copyright 2006 John Wiley and
Sons.
between the electronic charges ρ of two electrons with opposite
spin in H2 obtained by the square of the wave function Ψ (eqs
2a):
ΔEelstat(classical) = q1q2 /r12 (1)
ρ = |Ψ|2 (2a)
ΔEelstat(qc) = ∫ dτ1dτ2ρ1ρ2/r12 (2b)
The two curves are nearly indistinguishable at distances >2 Å
where the wave function overlap is negligible. At shorter
distances the electrostatic repulsion ΔEelstat(qc) (qc = quasi
classical) given by eq 2b is much less than the classical repulsion
between two point charges and approaches a finite value at r = 0
whereas the classical eq 1 leads to an infinite Coulomb repulsion.
The third curve in Figure 1 depicts the Pauli (exchange)
repulsion between two electrons having the same spin. It
becomes obvious that the onset of the Pauli repulsion,
depending on the overlap of the wave functions, takes place at
shorter distances but has a much steeper slope than the
Coulomb repulsion. The Pauli repulsion is the physical origin of
the loosely defined concept of steric repulsion between bulky
substituents. It also provides a quantum theoretical basis for the
VSEPR (Valence Shell Electron-Pair Repulsion) model of
Nyholm and Gillespie.25−27 The total Coulombic interactions
between neutral species are usually attractive, because of the
electrostatic attraction between atomic nuclei and electrons.28
This is discussed in more detail below.
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Figure 2. Copy of the figure by Heitler and London from their 1927
paper which shows the potential energy curves of dihydrogen calculated
classically (E11) and using the wave function Ψ (Eα and Eβ). Reprinted
with permission from ref 8. Copyright 1927 Springer Nature.
Figure 2 shows the original curves by Heitler and London8 for
the interaction between two hydrogen atoms. The energy curve
E11, which is based on the quasi-classical Coulomb interactions
between the superimposed atomic charge distributions, has only
a weak energy minimum of ∼0.5 eV at a rather long distance of
∼1.7 atomic units, while the curve Eα for the attractive
interactions that are calculated using the wave functions has a
much deeper potential of ∼2.5 eV at a more reasonable bond
distance of 1.5 atomic units. The curve Eβ refers to the repulsive
interactions between two hydrogen atoms where the electrons
have the same spin. The occurrence of two energy curves for the
interactions between the hydrogen atoms is a quantum
theoretical phenomenon that cannot be explained by classical
physics. This must be kept in mind when bonding models like
the Lewis electron pair, which are the results of human
interpretation of experiment and thus based on classical objects,
are used to explain chemical findings.
The essential finding of the Heitler−London work, which
features the very core of covalent bonding, might be presented in
a simplified way. We skip some mathematical details, in order to
extract the central message. Scheme 1 shows the quasiclassical
approach (eqs 3−5) for chemical bonding in H2, which employs
the electronic charge distribution ρ(H) of the hydrogen atoms
as starting point for the interatomic interactions. The calculation
using Coulomb’s law results in E11, which has only a shallow
energy minimum (Figure 2). The bottom part of Scheme 1
delineates the quantum theoretical approach, where the wave
function Ψ(H) is used as elementary physical quantity rather
than ρ(H) for the description of the electron. Since ρ(H) is the
square29 of Ψ(H) (eq 6), both ±Ψ(H) may be used for the
generation of the wave function Ψ(H2) (eq 7) in a simple one-
particle model. The electronic charge distribution ρ(H2) is then
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Scheme 1. Schematic Description of the Interatomic
Interactions between Two Hydrogen Atoms Using (a) a
Classical Approach and (b) a Quantum Theoretical
Approach
given by squaring |Ψ(H2)|2 (eq 8). The associated binomial in eq
9 gives the term ±2[c1c2 Ψ(Ha)Ψ(Hb)], which describes the
interference of the atomic wave functions that leads to attraction
(+ sign) or repulsion (− sign). The respective attractive and
repulsive energy terms are shown in eqs 10a and 10b. This result
comes from a quantum theoretical description of the interatomic
interactions leading to the curves Eα and Eβ in Figure 2. The
interference term Ψ(Ha)Ψ(Hb) is a pure quantum theoretical
expression, which does not have a classical analogue.
Chemical bonding is therefore a quantum chemical effect and
can be seen as caused by the interference of atomic/fragmental
wave functions. Chemical bonding is due to electron-sharing but not
due to electron pairing. There is a second aspect of covalent
bonding that is often misstated in chemistry textbooks and refers
to the contribution of kinetic and potential energies to the
energy lowering due to the formation of a chemical bond.
According to the virial theorem at equilibrium distances E = 0.5
V = −T, it follows that the change in the total energy E has the
same sign as the potential energy V, whereas the kinetic energy T
has the reverse sign. For the bond energy ΔEb thus holds ΔEb =
0.5ΔVb = −ΔTb. This agrees with the popular statement that the
bonding electrons, due to charge accumulation in the
interatomic region, are energetically stabilized, because they
are attracted by two nuclei. A close examination of the change in
the electronic structure of two atoms along the bond path reveals
that the formation of the chemical bond is rather complex and
exhibits a paradoxical behavior concerning the contribution of
the kinetic energy T and potential energy V. Figure 3 shows the
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alteration of E, V, and T for H2 as a function of the H−H
distance.
Figure 3. Energy curves of the total energy E, potential energy V, and
kinetic energy T as a function of the H−H distance. Reprinted with
permission from ref 42. Copyright 2019 Springer Nature.
When the hydrogen atoms approach each other, the kinetic
energy along with the total energy is at first lowered whereas the
potential energy rises. This is because the electronic charge
experiences a larger volume in the overlapping valence space.
The potential energy rises, because the “electron distance” to the
nuclei is longer than in the atoms. This is the region where the
actual bond formation mainly takes place. At shorter distances,
the effect of electronic charge depletion at the nuclei dominates
leading to shrinkage of the effective atomic radii. As a result, the
depleted charge in the core region experiences a stronger
attraction by the nucleus, which lowers V and increases T. The
latter process eventually overcompensates the reverse change of
T and V in the bonding region and yields an overall increase of
kinetic energy and lowering of potential energy at the
equilibrium distance. The conclusion is that the driving force
for the accumulation of electronic charge in the bonding region
associated with the formation of the chemical bond is the
lowering of the kinetic energy. This was shown for the first time
by Hellmann.30 After some controversy,14 it was finally
confirmed by Ruedenberg.31−36
The finding that the origin of covalent bonding is due to the
interference of the wave functions of the bonding atoms is not
restricted to dihydrogen, and it is not confined to nonpolar
bonds. It will be shown below that H2 is in many ways untypical
for covalent bonding, but the physical origin for covalence is the
same for all atoms. Ruedenberg and others have demonstrated
this in detailed theoretical studies.31−34 Electrostatic attraction,
exchange (Pauli) repulsion, and further factors contribute to the
intricate combination that yields a chemical bond, but the
interference of the wave function remains at the origin of
covalent bonding.
The following conclusions arise from this section:
• The physical origin of the covalent bond between atoms is
the interference of the atomic wave functions but not the
formation of an electron pair. Chemical bonding comes
f rom electron-sharing but not f rom electron-pairing between
atoms.
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• The driving force for the formation of a chemical bond is
the lowering of the kinetic energy of the accumulated
charge in the bonding region.
• The strength of the e−e repulsion as a function of the
distance exhibits a drastically different behavior when
electrons are considered as point charges compared to
orbitals. The Pauli repulsion between electrons that
possess the same spin is much stronger than Coulombic
repulsion in regions where the orbital overlap becomes
important.
• The frequent appearance of an electron pair in chemical
bonds is due to the Pauli principle. It may be reasonably
used as a model for depicting molecular structures and
chemical bonds (and particularly useful in explaining
organic reaction mechanisms), but it must not be
confused with the physical origin of the chemical bond.
3. HISTORICAL DEVELOPMENT AND PRESENT
SITUATION OF BONDING MODELS FOR
MAIN-GROUP COMPOUNDS: THE LEWIS
PARADIGM
The development of theoretical concepts and models to
understand the physical world is a fascinating chapter in the
history of mankind.37 Chemistry played a prominent role in the
endeavor to explain observations in nature and in experiments
and to formulate conclusions that may be used for future
predictions. Based on the corpuscular theory of matter, which
was not undisputed until the early 20th century, and following
the introduction of the periodic system of elements by
Mendeleev and Meyer, chemists designed symbols and formulas
as synonyms for characterizing substances that are composed of
atoms. The Scottish chemist Archibald Couper was the first who
in 1858 suggested a dash connecting two atoms as a symbol for a
chemical bond without any physical meaning assigned to it.38
The 19th century witnessed numerous suggestions for
explaining the ever-increasing number of experimental observa-
tions in terms of bonding models. The wealth of information
resulting from chemical research was used as source for a neural
network to produce helpful concepts that were improved or
dismissed by experimental results. Chemical research was
additionally fuelled by the fact that its products became the
foundation of the chemical industry that arose as an important
new commercial branch. But the concepts and models were
considered to have mere symbolic meaning rather than physical
relevance. Three-dimensional structures were only later assigned
to the chemical formula, most prominently by van’t Hoff, who
established together with Le Bel the tetrahedral model for
carbon compounds to explain the occurrence of enantiomers
and the phenomenon of optical activity. However, the question
about the physical foundation behind these models could not be
answered.
In 1916 Gilbert Lewis published his seminal work in which he
suggested that the symbolic dash between two atoms should be
identified with an electron pair.2 He also recognized that stable
molecules have mostly atoms that possess eight electrons in their
valence shell. Lewis introduced the cubic model for an atom
where the electrons are located at the corners of the cube. He
realized that the cubic atom may describe single and double
bonds but not triple bonds, for which the tetrahedron was a
better model. As mentioned above, Lewis was aware of the fact
that his electron-pair model violates the laws of classical physics
for electrostatic forces. The quantum theoretical laws for the
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electrostatic interaction between charged particles providing the
mathematical framework for the puzzling behavior of matter at
an atomic scale were introduced ten years later by Heisenberg9
and Schrödinger.10
The suggestions of Lewis were picked up by Langmuir, who
elaborated on the electron-pair model in a series of four papers
from 1919−1921.3−6 Langmuir coined the term “covalence” for
the chemical bond, and he formulated the octet rule for main-
group atoms along with the related 18-electron rule for
transition metals and the 32-electron rule for lanthanides. The
latter rules were later rationalized by quantum theory with the
occupation of the valence shells of the atoms. In 1923, Lewis
published the book Valence and the Structure of Atoms and
Molecules, where he extended his viewpoint on the electron-pair
bonding model.39 The book was partly written as a response to
the Langmuir papers, which received much attention and led
some chemists to articulate the “Langmuir-Lewis model”.40
Lewis stressed the importance of the electron pairing for
chemical bonding, saying “Whether we are dealing with organic or
inorganic compounds, the chemical bond is always such a pair of
chemical bonds.”39 The dogmatic adherence to the electron pair
as the origin of the covalent bond and a deeply rooted aversion
against quantum theory, which was at that time in an embryonic
state, may have contributed to his unwillingness to open his
mind for the upcoming important developments. In his book, he
called quantum theory “the entering wedge of scientific bolshevism”
but then he concedes “Quantum theory has been criticized for
f urnishing no adequate mechanism, but presumably the root of our
present problem lies deeper than this, and it is hardly likely that any
mechanism based on our existing modes of thought will suf f ice for
the explanation of the many new phenomena which the study of the
atom is disclosing”.39 It appears that Lewis was neither willing nor
prepared to accept the findings of quantum theory, which finally
came in 1927. His latest study solely devoted to the chemical
bond appeared in 1933,41 six years after the Heitler−London
paper about the quantum chemical nature of covalent bonding.
The very long paper, which does not have a single reference,
reads like a defense of the electron-pair model in spite of its
apparent deficiencies for describing some molecules. It seems,
however, that Gilbert Lewis himself recognized the limitations of
his approach. In the final statement of the 1923 book, he pointed
out that his model may have to be modified in the future and that
he wants “...to emphasize the necessity of maintaining an opening of
mind; so that, when the solution of these problems, which now seem
so baff ling, is ultimately of fered, its acceptance will not be retarded
by the conventions and the inadequate mental abstractions of the
past”.39 His request, which was perhaps inspired by recognizing
his own limitations, has not lost its timeliness until today.
An important contribution to the manifestation of the
electron-pair bond as fundamental model for chemical bonding
is the work of Linus Pauling. Unlike Gilbert Lewis, Pauling had
an open mind for quantum theory, which he studied during his
research stays in Europe in 1926 in the laboratories of Niels
Bohr, Arnold Sommerfeld, and Erwin Schrödinger. Like Gilbert
Lewis, he had an enormous knowledge of chemistry and he was
also acquainted with the newly emerging technique of X-ray
crystallography. Pauling blended the information from exper-
imental chemistry, quantum theory, and structural chemistry
into a far-sighted but also biased vision of molecular structure
and bonding. He published the results in a series of papers that
finally culminated in the epochal book The Nature of the
Chemical Bond, which was first published in 1939.11 The book
clearly shaped the vision of the chemical bond for generations of
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chemists until today. Pauling succeeded in the difficult task to
combine the classical viewpoint of the structure of molecules
familiar to experimental chemists with the information that was
provided by the rather exotic perspective of quantum theory. He
recognized a resemblance of the electron-pair model of Lewis to
the Heitler−London ansatz for the quantum chemical treatment
of H2, which uses an electron-pair function for the H−H bond,
and he developed his theory of resonating structures for the
description of molecules. The localized picture of valence bond
(VB) theory, which was introduced by Heitler and London,
appeared to him as far more suitable for chemistry as the
delocalized results of molecular orbital (MO) theory, which he
strongly opposed.
The opposition of Pauling against MO theory is in retrospect
difficult to understand for rational reasons, because the
advantages of the MO approach over the VB method for
explaining chemical phenomena soon became obvious. The
electronic triplet ground state of O219 and the peculiar stability
of aromatic compounds20 could easily be explained with the
symmetry of the MO wave function. Pauling did not recognize
the information that is provided by the symmetry of the wave
function, which later became an important reason for the
breakthrough of MO theory explaining molecular structure and
reactivity. It was mainly due to the pioneering FMO work by
Fukui21 and to the orbital symmetry rules by Woodward and
Hoffmann22 that MO theory became the leading source for
bonding models. A second reason for the present dominance of
MO theory is the development of computers and efficient
algorithms for solving the Schrödinger equation, where the
orthogonality of the orbitals make MO calculations substantially
faster than VB calculations.
More important for the present topic is the fact that MO
theory is neither in conflict with nor does it invalidate the
electron-pair model of Lewis. Quite on the contrary, the MO
method is even better suited for explaining molecular structures
in terms of Lewis structures than VB calculations, and it offers a
quantum theoretical foundation for writing molecules possess-
ing unusual bonds with the electron-pair model.42 At the same
time, it clearly shows the limitations of simple Lewis structures
for describing chemical bonding. The diatomic molecules Be2
and O2, which are discussed below, are prominent examples for
where the straightforward application of the Lewis paradigm fails
without using the symmetry of the underlying wave function.
Without knowledge of the orbital symmetry, there is no way to
understand why Be2 is essentially unbound with a rather tiny
dissociation energy of 2.3 kcal/mol and why O2 has a triplet
ground state. Dioxygen is also an example for a molecule where
the electronic structure may not reasonably be expressed by
Lewis structures. There is no Lewis formula that satisfies the
octet rule and the triplet state along with the double bond in O2.
According to the Lewis bonding model and the octet rule,
dioxygen should be a singlet with a classical double bond OO.
Lewis introduced a particular type of electron-pair bond,
which he used for a general definition of acids and bases that now
carry his name. He wrote that “a basic substance is one which has a
lone pair of electrons which may be used to complete the stable group
of other atoms and (...) an acid substance is one which can employ a
lone pair f rom another”.39 He elaborated this model in a later
publication in 1938, which focuses on acid and bases.43 Sidgwick
recognized the value of the dative bond for the description of
coordinative compounds, which he described in 1923.44 It was
further elaborated in his monograph published in 1927, where
he introduced the notion of donor and acceptor bonds and
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suggested an arrow as symbol for a dative bond A→B, as it is
called now.45 Sidgwick also showed that the peculiar dipole
moments of some molecules such as carbon monoxide, which
has its negative end at carbon, can be explained with the
direction of the donor−acceptor bond, which he sketched with
the formula .46 This explanation was later supported by
quantum chemical calculations.47 Pauling dismissed the concept
of dative bonds, because he found it inconvenient,11 which may
be the reason that the relevance of dative bonding in main-group
compounds has not been recognized for a very long time.
Haaland stressed the model of dative bonding in main-group
compounds in a review article that appeared in 1989, which was,
however, restricted to classical donor−acceptor complexes
mainly of group 13−15 adducts.48 The full potential of the
model of dative bonding in main-group chemistry came to the
fore in systematic theoretical studies of low-valent compounds
in the recent decade49 that led to the discovery of divalent
carbon(0) compounds (“carbones”)50−54 and related systems,
and contributed to the amazing development of subvalent main-
group chemistry.55,56 This is discussed in a dedicated section
below. The renaissance of the model of dative bonding was not
undisputed,57−59 but recent developments show that it is now
generally accepted as a valid description for the bonding
situation in main-group compounds that was already envisaged
by Lewis and Sidgwick.49,60−62
Finally, we want to comment on molecules that are
considered as species, which exhibit “unusual bonds”. The
origin of the unusual bonding situation is not always the peculiar
electronic structure but the difficulty to describe it with the
Lewis electron-pair model. A striking example is dioxygen O2,
which has an electronic triplet (X3Σg−) ground state. The
bonding situation can easily be understood with an orbital
interaction diagram. “Unusual bonding situations” may some-
times only indicate that the Lewis model is not suited for the
electronic structure, which may easily be understood by another
model such as the MO correlation diagram.63
The following conclusions arise from this section:
• The shared electron-pair bonding model is unsurpassed in
its simplicity for describing molecular structures, but it
must not be confused with the physical origin of chemical
bonding. The Lewis bonding model lacks the quantum
theoretical information about the symmetry of the wave
functions, which leads to problems particularly for
molecules with delocalized bonds and hypervalent
species.
• The choice of the best Lewis structure for a given
molecule with unusual bonds should be made in
conjunction with quantum chemical calculations. The
evaluation of the symmetry of the wave function, which is
provided by MO calculations, is very helpful for finding
the best description of the bonding situation.
• The distinction between electron-sharing bonding and
dative bonding, which was already introduced by Lewis,
then recognized by Sidgwick and later by Haaland, is a
very useful tool to characterize the nature of the chemical
bond.
4. QUANTUM CHEMICAL METHODS FOR
CALCULATING MOLECULAR STRUCTURES AND
PROPERTIES
It has become a standard procedure in chemical research to
supplement experimental results with quantum chemical
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calculations in order to elucidate the bonding situation in
molecules. This is often done with a mere presentation of the
calculated data without critical examination of the theoretical
method used. It is regrettable that the information which is
provided by the calculations remains often obscure and
questionable, because it is frequently given without knowledge
of the relevance of the calculated data and the approximations
used. In the following, we will sketch the most important
methods that are presently used in chemical research. We will
not discuss the details of the mathematical methods. Our focus is
not on the technical features of the quite sophisticated
approaches used by the quantum chemistry community; they
can be found elsewhere in the literature.64−66 We rather
emphasize the fundamental aspects of the three most important
methods, where we highlight the information that is given by the
calculations with respect to the nature of the chemical bond and
the relationship to the bonding models. The sheer presentation
of calculated numbers in publications is rather useless without a
critical examination of the relevance of the data obtained, which
requires knowledge about the approximations that are inherent
in the respective method.
The historically eldest quantum theoretical method is Valence
Bond (VB) theory, which was used by Heitler and London in
their pioneering study in 1927.8 It was the prevailing approach
for some decades, which is mainly due to the strong support by
Pauling.11 The advent of computers and the development of
numerical algorithms and codes showed that Molecular Orbital
(MO) theory is far better suited for quantum chemical
calculations, basically rendering VB methods obsolete for
numerical studies. Wave function based MO methods clearly
became the dominant approaches for quantum chemical
calculations during the 1970s. They were gradually replaced in
the past two decades by Density Functional Theory (DFT),
which is presently, in numerous different variations, the most
important tool for quantum chemical studies of larger
molecules.67 Examination of the basis of the Kohn−Sham
(KS) DFT calculations reveals that they are essentially
parametrized variants of the MO method, which is the reason
that some authors call them Density Functional Approximation
(DFA). We will use the more common term DFT for this
method. Because of the close resemblance of the fundamental
equations in wave function based MO and KS-DFT calculations,
we describe the two methods first before we introduce the basis
of VB calculations. The latter has lost its relevance not only
because of its computational drawback as already mentioned but
also because the apparent advance for the interpretation of
chemical bonding in terms of the electron-pair model of Lewis
has been lost with the development of the Natural Bond Orbital
(NBO) method by Weinhold introduced below.68−71
4.1. Molecular Orbital (MO) Theory
MO theory expresses the electronic wave function for the
electronic ground state of a molecule Ψ0MO as a sum of Slater
determinants ΦN (eq 11) where the first term Φ0 is usually
already a very close approximation to Ψ0MO. The sum of the
remaining terms runs over the singly (c1), doubly (c2), and
higher excited configurations of Φ0. The theoretical fundament
of MO theory can be grasped by understanding the elementary
steps for the formation of Ψ0MO (configuration interaction
procedure).
Ψ0 MO = c0 Φ0 + ∑ c1Φ1 + ∑ c2Φ2 + ∑ c3Φ3+...
(11)
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E0 MO = E0 0 + E01 + E0 2 + E0 3 + ... (12)
The associated energies are given by eq 12, where E0MO refers
to the energy of the electronic ground state, E00 is the Hartree−
Fock energy, and the remaining terms are the correlation
contributions of Nth order arising from a step-by-step variational
treatment. The first step in determining the MOs consists of a
linear combination of the atomic orbitals (LCAO) χa (eq 13)
which gives, via Hartree−Fock calculations (eq 14), the
molecular orbitals φi that are used to construct the Slater
determinant Φ0 as a product wave function (eq 15):
φi = ∑ cα χia
α (13)
Fiφi = εiφi (14)
Φ0 = |φ1φ2φ3 ... φN|
(15)
The order of eqs 13 and 15 indicates the basic difference
between MO theory and VB theory (described below): LCAO-
MO theory is a product of sums while VB theory rests on a sum of
products. MO calculations use orthogonal functions, which,
compared to VB theory, are much easier to implement into
computer programs leading to significantly faster algorithms.
This is the reason why quantum chemical calculations that strive
for numerical accuracy are nowadays mostly based on MO
theory; that is, much larger molecules can be calculated with
higher precision than with the VB method.
We want to point out that the molecular orbitals φi in the
Slater determinant Φ0 (eq 15), the so-called canonical MOs, are
a particular set of orbitals that are most commonly used, as these
have properties that make them well suited for chemical bonding
models. The symmetry of the orbitals was soon recognized as
important information that indicates the stability and reactivity
of molecules. Hückel realized that the peculiar stability of
aromatic compounds can be explained with the symmetry of the
π MOs, which was later formulated with the famous Hückel 4n +
2 rule. The delocalized picture of the canonical MOs was for
some time an obstacle for accepting it as a valid description of
chemical bonding for chemists, because it did not agree with the
localized picture of the electron-pair bond of Lewis. The
breakthrough came with the FMO model of Fukui,21 the advent
of the orbital symmetry rules by Woodward and Hoffmann,22
and the publication of several textbooks on MO theory after
1960.72−74
MO theory does not automatically yield delocalized MOs.
The canonical set of orbitals in the Slater determinant is only a
particular choice, because they provide the information that is
given by the symmetry of the orbitals. The orbitals can be
transformed via unitary transformations into equivalent MOs
that are subject to the chosen conditions. Thus, the delocalized
canonical MOs can be transformed to localized orbitals, which
closely resemble the electron-pair model of Lewis. It is not
correct to say that MO calculations necessarily yield delocalized
orbitals, which are difficult to associate with the Lewis electron-
pair model. On the contrary, the localized valence MOs exhibit
spatial extensions of the electron pairs that may be associated
with electron-pair bonds and lone pairs. However, the symmetry
information of the canonical MOs is lost and localized MOs do
not have an eigenvalue attached. Unlike localized orbitals,
canonical orbitals provide symmetry information and they
possess energy eigenvalues, which lead to the situation that
usually only the latter are used as models.
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However, the use of canonical MOs that construct the Slater
determinant Φ0 (eq 15) has a drawback: Only the construction
of the first component of the wave function Ψ0MO (eq 11) is
taken into account. Although the energy contribution of Φ0 is in
most cases >99% of the total energy, it may not be sufficient for
the bond energy, and thus, the use of Hartree−Fock orbitals φi
for chemical bonding may be questioned. It turned out, however,
that in most cases the MOs that arise from Hartree−Fock
calculations (eq 14) are sufficient for a qualitative discussion of
the bonding situation except for van der Waals interactions,
which are dominated by electron correlation. Nevertheless, they
have been replaced in recent years by the Kohn−Sham orbitals
φiKS that arise from DFT calculations, which are briefly
introduced in the next section.
4.2. Density Functional Theory (DFT)
The basis of density functional theory is the Hohenberg−Kohn
Theorem,75 which states that the ground state properties of a
many-electron system are uniquely determined by the electron
density ρ(r), depending only on the three spatial coordinates
and the external potential; hence, the total energy of the ground
state is a unique functional of the electron density. Unlike the
wave function based MO and VB theories, DFT takes the
density as the starting point of the calculations where the total
density of an N-electron system is given by the sum of the one-
electron densities. Thus, the result of a DFT calculation is (in
principle) not an approximate energy E0N as in MO calculations
but the correct total energy E0 (compare eq 12), provided that
the correct density ρ(r) and functional are known. It must be
realized that DFT does not focus on the formation of the
electron density ρ(r) but rather on the connection between the
density and the associated energy. The density ρ(r) is
considered as the starting point of DFT. But the work by
Heitler and London8 has shown that the chemical bonds in a
molecule can be described by the interference of wave functions.
The exact density ρ(r) can of course be obtained from the exact
wave function Ψ, but it can also be constructed from the Kohn−
Sham (KS)76 functions shown in eq 16, which are the working
horse of present DFT methods. Within KS theory the total
density of an N-electron system is simply the sum of one-
electron densities. The KS equations look similar to the
Hartree−Fock equations (eq 14), which are shown again in eq
17, and we use the superscript HF in order to distinguish them
from the Kohn−Sham equations:
F KSiφi KS = εi KSφi KS (16)
F HFiφi HF = εi HFφi HF
(17)
The crucial difference between the Kohn−Sham (KS)
equations (eq 16) and the Hartree−Fock (HF) equations (eq
17) lies in the expressions for the operators FKS and FHF.77,78 The
HF operator FHF contains well-defined terms for the kinetic and
potential energy of an electron and its average electrostatic
repulsion with the other electrons as well as the exchange (Pauli)
interaction with other electrons that have the same spin. This
leads to the HF energy E00, which is the first term in eq 12. The
individual correlation with the other electrons is neglected but
can be considered by the higher order terms in eq 12, which,
when included in a CI procedure, is quite computer time-
consuming. This is the well-known bottleneck of correlated ab
initio calculations.
DFT calculations try to rectify this problem by adding a
further term to the KS operator FKS that considers exchange-
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correlation through a functional. The expression for the Pauli
repulsion in FKS is however different from that in FHF. There are
further modifications in various different forms of the KS
operator FKS that have been developed over the past decades.78
There is now a rather large and still growing number of DFT
approximations available with different KS operators FKS that
strive at the same holy grail: To calculate the KS orbitals φiKS via
eq 16, which, after quadrature and summation, give a total
density ρ(r) that is as close as possible to the exact density. Once
this is achieved, all physical properties such as the ground state
energy can be obtained. The computational costs of such DFT
calculations are comparable to ab initio calculations at the HF
level, with the additional bonus that electron correlation is
already considered. The enormous progress which has been
made in the past two decades in developing DFT led to the
present situation where quantum chemical calculations are now
mainly performed using DFT with various functionals.79,80 One
important aspect that distinguishes DFT from MO theory must
be stressed, however. The quality and reliability of MO
calculations can stepwise be improved toward the exact solution
by using higher correlated methods and larger basis sets. This
leads eventually to the correct physical properties in agreement
with experiment, albeit at steeply increasing computing costs.
DFT calculations at a certain level can, at the moment, not be
improved in this fashion.81
We do not wish to discuss the pros and cons of various DFT
approximations here. We rather focus on aspects relevant for the
present topic, which is the nature of the chemical bond. The
Kohn−Sham orbitals φiKS were originally considered a mere
technical detail that has accessory character for obtaining the
exact electron density ρ(r). Inspection of the shape and the
energy levels of φiKS along with their atomic orbital composition
showed that they are closely related to HF orbitals φiHF, with the
additional bonus that the φiKS are associated with the exact wave
function Ψ0 while the φiHF are associated with the HF wave
function Φ0 (eq 11). This led to the present situation that KS
orbitals φiKS are routinely used for the analysis of the electronic
structure and bonding situation in molecules in the framework
of qualitative molecular orbital theory, which originally
employed semiempirical methods or Hartree−Fock orbitals.
Most of the works, which are discussed in this review, are
therefore based on DFT calculations and the analysis of Kohn−
Sham orbitals φiKS.78−84
There is one important aspect of DFT that is very important
for the present topic. There are molecules which possess unusual
electronic structures in the sense that they are poorly described
with MO methods that use only one determinant as leading
configuration (static correlation). Such molecules usually pose
problems for traditional DFT methods, which so far are
restricted in the wave function picture to single determinant
variants. Fractional occupation numbers can be, however, used
and, similar to wave function based methods, multideterminant
DFT methods are being developed to solve problems such as
double-counting electron correlation.85−88 These are interesting
developments, but they have not yet reached the stage of routine
methods. Accurate wave function based MO methods still play
an important role for checking the reliability of DFT calculations
for physical properties, particularly in molecules that are not well
described with one Lewis structure. Approximate DFT methods
as we use them today cover electron correlation in an
unspecified way as a consequence of their semiempirical nature.
Therefore, they cannot be used as a black box, and the results
should always be checked for a smaller test set against high
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quality wave function results. We warn against an indiscriminate
use of DFT calculations for analyzing the bonding situation in a
molecule.
4.3. Valence-Bond (VB) Theory
Unlike the MO method, where the wave function Ψ0MO is
assembled as the product of one-electron functions φi yielding
the Slater determinant Φ0 (eqs 11 and 15), the VB wave function
Ψ0VB is expressed as the sum of localized two-center product-
functions (λaλb).89−91 The occupation of the product-functions
λaλb by two electrons of opposite spins gives the electron-sharing
covalent term (λa−λb) (“Heitler−London” term) and the two
ionic terms (λa|− λb+) and (λa+ λb|−). The basic VB expansion,
which considers all possible products in the molecule, is given by
eq 18, where the summation runs over all electron pairs in the
molecule:90
Ψ0 VB = ∑ c1(λa−λ b) + ∑ c2(λa|−λ b+) + ∑ c3(λa+λ b|−)
(18)
As mentioned above, the use of orthogonal orbitals in MO
calculations leads nowadays to much faster algorithms in
computer programs than VB methods, where overlapping
hybrid orbitals are employed. VB methods do not play a role
in theoretical research of larger molecules, which strives for
numerical accuracy. They were, however, favored over MO
theory by Pauling, because they appear at first sight to be more
closely related to the electron-pair model of Lewis. The first term
in eq 18 could be identified with the covalent electron-pair bond,
whereas the second and third terms give the ionic bonding
contribution. The coefficients c1 and c2/c3 appear as ideally
suited to indicate the covalent and ionic character of a bond.
This was suggested by Pauling in his book The Nature of the
Chemical Bond, which shaped the understanding of chemical
bonding of many chemists for decades.11 The development of
computers and algorithms for carrying out VB calculations,
however, made it possible to check the validity of this qualitative
model. It turned out that there are molecules such as F2 where
neither the covalent term (λa−λb) nor the ionic terms (λa|− λb+)
and (λa+ λb|−) alone yield the correct bonding energy. It is the
mixing of the two terms that leads to a quantitative account of
the bond energy. This makes the interpretation of the VB terms
in eq 18 for indicating covalent and ionic bonding questionable.
The Lewis electron-pair bonding model refers to the total bond
while the covalent term (λa−λb) covers only part of the total
energy of a VB calculation.92 The nature of the chemical bond in
F2 and other diatomic molecules is discussed further below. The
conclusion is that VB methods are not necessarily better suited
for the interpretation of the chemical bond in terms of the Lewis
bonding model.
The following conclusions arise from this section:
• Molecular orbital calculations provide a reliable frame-
work for the identification of the electronic structure of a
molecule, but they may become quite expensive when a
single determinant calculation is not adequate for the
situation.
• The results of MO calculations can easily by expressed in
terms of Lewis structures by using localized MOs.
• Present DFT calculations can be considered as para-
metrized MO calculations. They are much more efficient,
and they often give very good results at lower costs than
Hartree−Fock based MO calculations. However, they
should not be used as black box methods, and the results
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should always be checked for a smaller test set against high
quality wave function results.
• VB calculations are more cumbersome compared to MO
and particularly KS-DFT calculations. The identification
of the leading terms of VB calculations with covalent and
ionic bonding has no physical fundament.
5. QUANTUM CHEMICAL METHODS FOR ANALYZING
THE CHEMICAL BOND IN MOLECULES
It has become a standard part, also in experimental work, to
present the results of quantum chemical calculations in
conjunction with a breakdown of the calculated numbers in
terms of chemically meaningful information about the bonding
situation and electronic structure in the molecules. There are
several methods available, which serve as a bridge between the
computed numbers of the quantum chemical calculations and
the heuristic bonding schemes such as the Lewis model. In the
following, we present a short summary of the approaches and
basic features of the most common methods, which should be
understood in order to prevent misinterpretation of the results.
Reasonable conclusions about the bonding situation in a
molecule are only possible when the most important details of
the sophisticated algorithms and the inherent assumptions,
which are intrinsically coded in the algorithms, are known. A
mere presentation of the calculated numbers without knowledge
of how they were obtained is meaningless.
Numerous charge- and energy-partitioning methods have
been developed over the course of time. The five conditions
given in Scheme 2 should be met by a partitioning procedure, in
order to provide a meaningful interpretation of the vast
complexity of chemical observations in terms of a bonding
model.
Scheme 2. Five Conditions That Should Be Fulfilled by a
Model for a Chemical Bond
5.1. Natural Bond Orbital Method (NBO)
The presently most popular tool for a bonding analysis of
molecules is the NBO (Natural Bond Orbital) method by
Weinhold and co-workers.68−71 It was introduced in the 1980s
and has been further developed in the course of time during
which it underwent significant changes.93 Thus, the results of an
early variant of the NBO program may be quite different from
those of a newer version. The goal of the NBO method is to
provide the most reasonable Lewis structure for a calculated
molecule along with information about the polarity of the bond
as well as the hybridization of the atoms and their partial charges.
The problem of determining the best Lewis structure is that
subjective criteria are taken into account when selecting the
mathematical steps and computer algorithms. This is true for
any chemical bond model. It is adamantly important that the
subjective criteria must be known when the results are
interpreted and compared with the values of other methods.
The NBO method takes the one-electron density matrix,
which is given by a quantum chemical calculation, as starting
point for the partitioning procedure. Because the NBO method
uses the density ρ instead of the wave function Ψ as initial point,
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it may be used in conjunction with any correlated ab initio
method or DFT calculation. This is a strong point of the
method. But there are two little known aspects of the NBO
method, which may lead to debatable results. One aspect
concerns the choice of the atomic valence orbitals, which are
considered for the formation of the molecular orbitals. The
NBO algorithm makes a preselection of those atomic functions
that are considered as genuine valence orbitals and those who
are termed Rydberg functions. The two sets are differently
treated in the subsequent algorithms, where the Rydberg orbitals
are technically treated with lower priority, which leads to biased
results. The division of the atomic orbitals into the two sets of
atomic functions is the subjective choice of the authors. Thus,
the outcome of NBO calculations is not “natural”, it is rather the
consequence of what the authors consider to be “reasonable”.
The NBO method considers only those outermost atomic
functions as genuine valence orbitals, which are occupied in the
electronic ground state of the atom. Thus, the NBO algorithm
considers the alkali and alkaline earth atoms having a (n)s
valence shell and the group 13−18 atoms to possess a (n)s(n)p
valence shell. The question whether the octet rule is valid for
main group atoms cannot be addressed in NBO calculations,
because the answer is already coded into the algorithms.94 The
above criterion leads to a critical situation for transition metals,
which have only an (n)s(n − 1)d valence shell. The latter choice
leads to a 12-electron rule rather than 18-electron rule for
transition metal complexes, because the (n)p AOs are only
treated as Rydberg orbitals.95−97 This has been criticized by
several authors, because the 18-electron rule is well established
in transition metal chemistry.98−100 Very recently, the transition
metal compounds [(CO)3Ni-E]− (E = Li − Cs) were reported,
where the covalent Ni−E bond at the nickel end comes mainly
from the Ni(4p) AO.101 The NBO calculations using version 6.0
do not give a faithful description of the Ni−E bonds. But even
for main group atoms, the preselection of valence orbitals
according to the NBO method can sometimes become
questionable. It was lately shown that the heavier earth alkaline
atoms M = Ca, Sr, Ba form strongly bonded octa-carbonyls
M(CO)8 using their (n − 1)d orbitals, which challenge the
restriction of the valence orbitals to (n)s functions.102
The second critical aspect concerns the algorithms of the
current eight orthogonalization steps, which have changed
during the different versions of NBO and sometimes lead to
inconsistent results when different versions are used. Early
versions of the program showed that the 3d participation of
sulfur in the bonding in SF6 is rather small, which agrees with the
general notion that d-AOs of the heavier main-group atoms are
polarization functions and that the model of hypervalence in
such compounds should be discarded.103 However, the recent
version NBO 6.0 surprisingly gives Lewis structures for SF6 with
perfect sp3d2 hybridization. A similar result is obtained for PF5,
which, according to NBO 6.0, has sp3d hybridized P−F bonds.
This is likely due to the projection operator in the NBO version
6.0, which yields an inappropriate hybridization for SF6 and PF5.
This has been fixed in the latest version NBO 7.0, which was
distributed while this review was written. The problem remains
that the biased treatment of the outermost atomic orbitals and
the technical details of the orthogonalization steps may lead to
results which should be checked in comparison with other
methods that are based on different partitioning schemes.
Whatever method is used, it holds that one should know the
details of a method in order to make a reasonable statement. The
aim of the NBO method is to propose a suitable Lewis structure
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but not to provide information about the electronic structure of
a molecule.
The NBO method was further developed toward the NRT
(Natural Resonance Theory) method, where energy expressions
for the intramolecular orbital interaction were suggested.104−106
The NRT was met with immediate scepticism,107 and the energy
values that are provided should be taken with some caution. The
NBO method focuses exclusively on orbital interactions in a
molecule. Electrostatic interactions and Pauli repulsion are only
indirectly considered. This may lead to conflicting interpreta-
tions about chemical bonding when other methods are
employed that include all physical forces.108−110 A strong
point of the NBO method is the finding that the numerical
results are usually rather insensitive to the level of theory, which
is of great advantage compared with the rather outdated
Mulliken population analysis whose results are plagued by large
variations when different basis sets are used.
An extension of the NBO method to molecules that exhibit
strongly delocalized bonds, such as electron deficient boron
compounds, has been developed by Boldyrev and co-workers.111
The Adaptive Natural Density Partitioning (AdNDP) method
describes N-center-two-electron bonds where N gives the
number of atoms to which the two-electron bond should be
assigned. The AdNDP method has been found to be particularly
useful for the description of organic and inorganic molecules and
clusters where the standard NBO method is less suitable. A
reformulation of the AdNDP approach has recently been
introduced by Pendás and Francesco, which provides Lewis
structures from real space analyses of general wave functions.112
A warning shall be addressed when the results of a bonding
analysis are judged by their agreement with “chemical intuition”.
The vaguely defined concept of chemical intuition, which refers
to the wealth of experimental experience in chemistry, may be
helpful as a guideline for future experiments and for the design of
a specific bonding model, but it is very questionable when it
comes to a physical interpretation of chemical bonding. As
discussed above, chemical bonding can be regarded as a
quantum theoretical phenomenon due to the interference of
wave functions. Quantum theory and chemical intuition often
do not fit together well, since human sensory perception, like
classical physics, is limited in space and time. Both quantum
theory and relativity are often at odds with the human mind and
intuition and may perhaps only be accessible through
mathematics. The difficulty of getting along with quantum
theory was suitably expressed by Niels Bohr: “Those who are not
shocked when they f irst come across quantum theory cannot possibly
have understood it”.113
5.2. Quantum Theory of Atoms in Molecules (QTAIM)
The NBO method is a charge-partitioning procedure that aims
at the division of the wave function Ψ into atomic regions. In
contrast, the QTAIM (Quantum Theory of Atoms in Molecules)
developed by Bader is based on a topological analysis of the
electron density ρ(r) into atomic basins.114 The mathematically
well-defined QTAIM method avoids some shortcomings and
problems of wave function based partitioning schemes. Using
the first derivatives (gradient field) ∇ρ(r) and second
derivatives (Laplacian) ∇2ρ(r) of the electron density, physi-
cally well-defined atomic regions and interatomic bond paths
may be identified, which typify a molecular structure by the zero-
flux surfaces that separate the atomic basins. The zero-flux
surfaces are defined as the gradient vector field whose
trajectories of ∇ρ(r) do not vanish at the atomic nuclei but at
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the bond critical point rb, which is a signature of a bond path. A
bond critical point rb has two negative and one positive
eigenvalues of the second derivatives of ρ(rb). Other critical
points at which the gradient of the electron density ∇ρ(r)
vanishes define rings and cages. The bond path is the trajectory
which belongs to the positive eigenvalue connecting the bond
critical point rb and the bonded atomic nuclei. Thus, the
QTAIM method gives a physically sound description of the
skeletal structure of the molecule in terms of atomic nuclei and
chemical bonds, which has been proven useful for a variety of
chemical systems.115
The QTAIM method is possibly the physically best founded
theory for chemical bonding, providing a rigorous quantum
theoretical proof that the model of discussing the chemical
behavior of a molecule in terms of atomic properties is justified.
Problems arise when the QTAIM results are connected to the
manifold of chemical observations, which are often more
meaningfully described with heuristic orbital models. As
mentioned above, the wave function and the orbitals exhibit
important information through their symmetry, which is lost
when only the electron density ρ is used instead of Ψ. This
makes the QTAIM method perhaps less powerful for making
predictions of chemical reactions. Another problem is the use of
the bond critical point rb as an indicator of a genuine chemical
bond. Diatomic He2 is a weakly bonded van der Waals complex
with negligible interference of the atomic wave functions, and
thus, it has no covalent bond. QTAIM calculations indicate a
bond critical point and a bond path just like in H2. This was
recognized by Bader, who clearly stated that “bond paths are not
chemical bonds”.116 On the other hand, there are molecules
where by visual inspection of the electronic structure one would
ascribe a covalent bond between two atoms but there is no bond
path.117,118
There has been theoretical work to distinguish different types
of chemical bonds that possess a bond critical point using
QTAIM parameters. The most successful one goes back to the
investigations by Cremer and Kraka, who suggested that the
energy density at the bond critical point H(rb) is a useful
criterion for defining the nature of a chemical bond.119
According to the Cremer−Kraka criterion, a covalent bond
between two atoms A and B is defined by the existence of a zero-
flux surface and bond critical point rb between the atoms
(necessary condition) and a negative and thereby stabilizing local
energy density H(rb) (suf f icient condition). H(rb) will be close to
zero or positive if the interaction between A and B comes from
the electrostatic or dispersion forces. This approach has been
found very helpful for the bonding analysis between electro-
negative atoms.120,121 But the numerical absolute values may
become very small when bonds between heavy atoms are
involved and the degree of covalent bonding is not directly
available from the values of H(rb).
In spite of the caveats, it may be stated that the QTAIM
method has been established as an important method to
elucidate the electronic structure not only in molecules but also
in solids.122 Inspection of the Laplacian distribution of the
electron density ∇2ρ(r) provides valuable information about the
areas of charge depletion and charge accumulation in a
molecule, which come from the interatomic interaction. The
combination of QTAIM calculations with the results of an MO
analysis is a very powerful tool, which helps to express the
bonding situation in a molecule with an appropriate model.
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5.3. Energy Decomposition Analysis and Natural Orbitals
for Chemical Valence (EDA-NOCV)
The NBO and QTAIM methods are charge-partitioning
techniques, which divide the electronic structure of molecules
into atomic regions. There are complementary methods that
first break up the total energy of a molecule into fragments,
which are then reassembled in a stepwise fashion where each
step is assigned to a particular type of interaction. The choice of
the fragments is determined by the question of interest. Trivially,
in a diatomic molecule X2 the two atoms are chosen as
interacting fragments, but already when a heteroatomic species
such as LiF shall be analyzed, it may be more useful to choose the
ionic fragments Li+ and F− for the bonding analysis. This seems
to make the method somewhat arbitrary and therefore
questionable, but the possibility of using different fragments
for the bonding analysis provides more flexibility that may be
used to address different questions about the bonding nature.
Thus, the choice of neutral Li and F as interacting fragments
includes all changes along the bond formation between the
isolated atoms toward LiF, whereas the choice of the ions Li+
and F− addresses the question about the nature of the eventually
formed bond. These are two different questions, which have two
different answers that can be addressed by choosing different
fragments.
The EDA-NOCV method123,124 is a combination of the EDA
(Energy Decomposition Analysis) method, which goes back to
initial ideas by Morokuma and Kitaura125 and later by Ziegler
and Rauk,126 and the original charge-partitioning method
NOCV (Natural Orbitals for Chemical Valence) by Mitoraj
and Michalak.127,128 It has been proven as a very powerful tool
for bonding analyses, because it considers all types of physical
interactions, which eventually sum up to the experimentally
observable bond dissociation energy (BDE). In particular, the
further partitioning of the orbital (covalent) term into pairwise
orbital interactions has been proven very helpful, because it
provides a quantitative expression of the FMO model of Fukui21
and the orbital symmetry rules of Woodward and Hoffman.22 A
nice feature of the EDA-NOCV model is that the orbital
interactions are not only given in terms of numbers, which
indicate their strength, but the associated charge migration can
visually be shown. In the following, we present the most
important aspects of the EDA-NOCV method. A more detailed
discussion of the method and its application has been given in
recent review articles.129,130 At the present time, EDA-NOCV
analyses can only be carried out using DFT or Hartree−Fock
calculations. Since correlation energy is missing in the latter
method, more meaningful results are obtained with DFT
approaches. The results do not change very much when different
functionals are employed.
The focus of the EDA approach is the instantaneous
interaction energy ΔEint of a bond A−B between two (or
more) fragments A and B in the particular electronic reference
state and in the frozen geometry of AB.131,132 It is very important
to recognize the correct electronic reference states of the
fragments in order to provide a meaningful analysis of the
interactions A−B. In doubtful cases, one may carry out EDA
calculations with different electronic states of the fragments and
compare the results. Those fragments, which give the smallest
energy change during the bond formation step, are the most
useful species for the bonding analysis.
The interaction energy ΔEint is divided into three main
components, which are sometimes augmented by a fourth
expression for dispersion (van der Waals) interactions:
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ΔEint = ΔEelstat + ΔEpauli + ΔEorb + (ΔEdisp) (19)
In the first step of the EDA procedure, the fragments A and B
are superimposed with their frozen densities at the geometry of
the molecule AB, which gives the quasi-classical electrostatic
interaction between the unperturbed charge distributions of the
prepared fragments ΔEelstat. The term is usually attractive,
because the frozen charge densities of the fragments overlap and
thus penetrate each other, which induces attraction with the
atomic nuclei of the other fragment.28 The overlapping densities
may have electrons that have the same spin, which according to
the Pauli principle is not allowed. This is rectified in the second
step of the EDA procedure, where the superposition of the
unperturbed electron densities of the isolated atoms is subject to
antisymmetrization (operator  ) and renormalization (constant
N), which gives the product wave function Ψ0 = N Â [ΨA(α)
ΨB(β)] still without interference of the fragment wave functions
ΨA(α) and ΨB(β). The energy term ΔEPauli, which is calculated in
the second step, accounts for the electron−electron repulsion
due to the orthogonality requirement of the orbitals. The final
term ΔEorb accounts for the formation of covalent bonding via
interfragment mixing of the orbitals but also for the polarization
within the fragments via intrafragment orbital mixing. Polar-
ization and charge transfer between the fragments are not
separated in the EDA approach.
If the two fragments of the chemical bond are in an
electronically excited state or if they have more than one
atom, there is an electronic and possibly a geometric relaxation
of the fragments during bond rupture into the equilibrium
geometry of the fragments, which corresponds to the
preparation energy ΔEprep. If the energy value is added to
ΔEint, one obtains the bond dissociation energy De, which is by
definition the negative value of the total bond energy ΔE:
ΔE ( = −De) = ΔEint + ΔEprep (20)
Although the individual terms in eqs 19 and 20 are not
observable quantities, the sum of them gives the experimentally
measurable bond dissociation energy. The absolute value of
ΔEint is a faithful expression for the intrinsic bond strength,
whereas the De values are affected by the geometrical and
possibly the electronic relaxation of the fragments. There are
molecules where the fragments A and B are lower in energy than
the molecule AB, which makes the De values useless for
estimating the bond strength A−B. This holds in particular for
high-energy materials and explosives where bond breaking is a
highly exothermic process. It is thus advisible to use the
interaction energy ΔEint for comparing the bond strength of
molecules.
There are cases where the electronic state of the fragments
used in the bonding analysis is not obvious. For example, N-
oxides R3NO might be described with a dative bond R3N→O or
with an electron-sharing single bond R3N+−O− or even a double
bond R3NO.133 The EDA method can be used to suggest the
best description according to the electronic structure, by using
the fragments in the respective electronic state in the actual
calculation. Those fragments, whose energy changes the least
during bond formation, appear the best choice for the
representation of the bonding situation. The smallest absolute
value of the orbital term ΔEorb may be used as a measure for the
best Lewis description of a molecule. This procedure has been
proven very helpful in a variety of compounds where the
bonding situation is not directly clear.49,134−146
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There is one important aspect of the ΔEelstat term in the above
EDA method that deserves to be discussed. The partitioning
scheme uses overlapping spheres of the atomic charge
distributions, which means that some electronic charge in the
molecule that is close to the nucleus of atom α is assigned as
coming from atom β. This may appear odd for human
imagination that is shaped by senses, which are trained by
classical hard objects. If one assumes the atoms are spheres with
impenetrable surfaces it seems more “reasonable” to cut a
molecule into atomic pieces by sharp boundaries as for instance
in the IQA (Interacting Quantum Atoms) model,147−150 which
is based on Bader’s QTAIM definition of separated atomic
basins.114 However, in quantum theory, an electron is described
by a wave function, which has an exponentially decreasing but
finite value even at larger distances and so has its square, which
gives the charge density of the electron (see below). Thus, for
example in N2, an electron of Nα has a finite density also close to
the nucleus of Nβ. The estimate of Coulombic interactions using
interpenetrating charge distributions in the EDA method thus
appears as a physically reasonable approach consistent with
quantum theory, which is commonly used in many theoretical
approaches, such as Mulliken analysis, Natural Bond Orbital
analysis, Hirshfeld partitioning,151 etc. On the other hand, the
wave function of an electron of Nα in N2 is subject to
interference with the wave functions of the electrons of Nβ. This
leads to some ambiguity in assigning the charge in a molecule
that comes from the interfered wave functions to a particular
atom. In conclusion, the many models of interpenetrating
charges as well as strictly separated charges may all appear more
or less physically reasonable.
The NOCV scheme127 divides the orbital interaction term
ΔEorb in the EDA-NOCV approach into pairwise contributions
of interacting orbitals of the two fragments. The starting point is
the deformation density Δρ(r), which is the difference between
the densities of the fragments before and after bond formation.
The deformation density Δρ(r) can be expressed in terms of
pairs of complementary eigenfunctions (ψk ψ−k) with the
eigenvalues υk and υ−k that possess the same absolute value but
opposite sign. The absolute numbers of the eigenvalues υk are a
measure for the magnitude of the charge transfer:
Δρ(r) = ∑ υk[−ψ 2−k(r) + ψ 2k(r)] = ∑ Δρk(r)
k k (21)
The NOCVs ψk and the associated eigenvalues υk are obtained
through diagonalization of the difference density matrix ΔPμν of
the system. Equation 21 facilitates the expression of the total
charge deformation Δρ(r) that goes along with the bond
formation in terms of pairwise charge contributions Δρk(r)
which come from particular pairs of (NOCV) orbitals. The total
orbital interaction ΔEorb may likewise be derived from pairwise
orbital interaction energies ΔEkorb which are associated with
Δρk(r):
ΔEorb = ∑ ΔEk orb = ∑ υk[−FTS−k ,−k + FTSk ,k ]
k k (22)
Experience has shown that the ΔEorb term of the EDA-NOCV
approach has usually only a very small number of significant
contributions of ΔEkorb, which makes it possible to identify
specific orbital interactions that lead to a chemical bond. This
connects the results of the EDA-NOCV method with classical
models of orbital interactions63 and with the Lewis electron-pair
model.152 Numerous examples where the EDA-NOCV method
proved helpful for a variety of main-group compounds134−146
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and transition metal complexes153−163 have been reported in
recent years. For a fruitful and enlightening discussion about
different results of the NBO method and EDA-NOCV
calculations on the nature of bonding in transition metal
compounds, we refer to two recent papers by Weinhold and co-
workers.164,165
The following conclusions arise from this section:
• There are several powerful analytical tools available which
extract information from quantum chemical methods
aiming at an understanding of the numerical results in
terms of a bonding model. But the user must be aware of
the details of the methods in order to provide a
meaningful interpretation of the results of the charge-
and energy-partitioning schemes.
• The NBO method has been designed to extract the best
Lewis electron-pair description of the molecular elec-
tronic structure. The atomic orbitals are not identically
treated; the results are biased toward a localized electron-
pair bonding model favoring preselected atomic orbitals,
which is considered by the program designers as
reasonable. The NBO method explicitely focuses only
on orbital interactions; other interatomic forces such as
Coulomb forces are not directly taken into account.
• The QTAIM method takes the electron density as starting
point for the analysis of the electronic structure. The
information that comes from the symmetry of the orbitals
is not considered. It provides a direct connection between
the physical description of interatomic interactions and
the electronic structure.
• The EDA-NOCV method is a combination of charge- and
energy-partitioning scheme. It provides a quantitative
interpretation of the chemical bond in terms of physically
meaningful contributions. The NOCV method is a bridge
between quantum chemical calculations and the FMO
model of Fukui and the orbital symmetry rules by
Woodward and Hoffmann. The strength of the orbital
interactions can be expressed numerically, and the
associated charge deformation can be visualized with
the help of the deformation densities.
• All analytical methods have their strengths and weak-
nesses. It is advisible to compare the results of several
methods in order to give a reasonable interpretation of the
bonding situation. The results of the bonding analysis
suggest a model description, which helps to understand
the experimental results in the framework of an ordering
scheme that is based on quantum chemical calculations.
But bonding models are not right or wrong; they are more
or less useful.
6. PHYSICAL REALITY AND CHEMICAL BONDING
MODELS
A frequent topic of controversial discussions among chemists is
the relationship between physical reality and chemical bonding
models. This holds in particular for models that are derived from
quantum chemical calculations such as the NBO and EDA-
NOCV methods, which quantitatively define expressions related
to the chemical bond that are given in terms of calculated
numbers. It is sometimes criticized that these numbers cannot
be measured by experiment and, therefore, they would not have
any physical meaning. Moreover, different definitions of
equivalent terms such as atomic partial charges or bond orders
may lead to very different values and sometimes even contradict
8794
Review
each other. It would be much better to rely only on measurable
quantities and on physical observables.
We think that such criticism stems from a misunderstanding
of the role and the relevance of bonding models and physical
theory in chemistry. It is also based on a questionable definition
of observables and physical reality, whose understanding has
profoundly changed with the advent of quantum theory. The
charge and mass of an electron are fundamental constants which
enter the Schrödinger (or Dirac) equation, which then are used
to calculate properties to very high accuracy in perfect
agreement with experiment. It is often said that the wave
function does not correspond to a quantity which can be
measured; it is a purely mathematical construct to describe the
electronic charge distribution. This led to a debate between
Heisenberg and Einstein: “One cannot observe the electron orbits
inside the atom. [...] but since it is reasonable to consider only those
quantities in a theory that can be measured, it seemed natural to me
to introduce them only as entities, as representatives of electron
orbits, so to speak” (Heisenberg). “But you do not seriously believe
that only observable quantities should be considered in a physical
theory?” (Einstein).166 But the one-particle density ρ obtained
from the wave function is also a mathematical construct, which is
used to describe experimental results. In this case, however, the
charge density can be probed experimentally as it is done for
example in X-ray diffraction. Since the outcome of a Diels−Alder
reaction can only be explained with the help of the symmetry of
the wave function Ψ, which uniquely identifies the interacting
species, it acquires the quality and the status of a physically
relevant entity that becomes evident by the reaction product.
Note that a complete wave function of a particle is a valid
expression containing all information about its physical
properties.
We want to make a reference to a recent perspective on
quantum mechanics and chemical concepts by Clark, Murray,
and Politzer (CMP).167 Although the focus of their work is on
noncovalent bonding, the central topic of their work has much in
common with the present article. The authors cite in the
beginning a statement by Ivanic, Atchity, and Ruedenberg
whose final words nicely sum up the central theme “...the
resolution of molecules in terms of atoms is not f undamental to
rigorous physical theory”.168 CMP rightfully point out that “the
distinction between what is mathematical modeling and what is
physical reality may become blurred; the model may be taken to
represent reality. This can be misleading and conf using.”167 We
agree, but the situation becomes a bit complicated when the
status of the wave function is concerned. The authors argue that
the electron density represents physical reality but not the wave
function. They quote Schrödinger, who warned against using the
wave function for the direct interpretation of physical
observations.169 The pioneers of quantum theory are known
not only for their ground breaking contributions to physics but
also for their limited acceptance of the outcome of their theories.
Einstein never accepted quantum mechanics as a valid physical
theory, and Dirac wrongly suggested that relativistic effects are
negligible for chemistry. The direct relevance of the symmetry of
the wave functions for chemical reactions was not obvious when
Schrödinger made his statement in 1926.169 The consideration
of the wave function or electron density as the basis of the
physical reality of matter can be seen as representing the
continuous versus atomistic theory of the universe. They are
rather complementary and not mutually exclusive. It is often said
that the present generation of scientists is standing on the
shoulders of giants. But this enables us to see further than they
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could, and we should not be afraid of challenging traditional to faciliate the comparison of molecules and reactions.
viewpoints. If one only repeats earlier findings, this means that Different tools can be applied to achieve a better
nothing new has been learned. understanding; their choice may depend on personal
The numbers, which come from chemical bonding models preferences and training. Different results and different
such as NBO or EDA-NOCV, arise from a breakdown of Ψ into views from different methods should be analyzed in the
fragments, which are defined via the particular charge- and light of the particular decomposition scheme, whose
energy-partitioning method. They are clearly not observables in suppositions and technical implementations must be
a quantum mechanical sense. Their relevance comes exclusively known for a meaningful interpretation of the results.
from their ability to construct an ordering scheme, which helps
to divide the enormous complexity of chemical reactions and 7. SELECTED EXAMPLES OF CHEMICAL BONDS IN
molecular structures into specific classes and groups. Histor- MAIN-GROUP COMPOUNDS
ically, this was done by the finding that certain molecules exhibit In the following, we discuss the chemical bond in selected main-
similar behavior. Heuristic notions were suggested such as group compounds, which serve as examples for the wide variety
aromaticity, conjugation, nucleophilicity, formal charge, etc. of molecules that possess different types of bonds. We try to
Although their definition is vague, these models are crucial for cover a wide range of bonding, which may be used as templates
bringing order into the pandemonium of experimental results. for other species. The goal of this section is to show how modern
Bonding models are vital for chemical research, because methods of bonding analysis may be used to (a) elucidate the
otherwise there would not be any systematic ordering of the nature of the interatomic interactions and (b) express the bond
infinite number of molecules and reactions. If one would explain in terms of a model that agrees with the physical mechanism of
chemical results only in terms of physical observables (including the bond. The latter part may lead to conflicting results with
the wave function) without bonding models, it would result in a earlier work presented in textbooks, because previous studies
huge table with data that do not provide any intuitive were often based on ad-hoc assumptions that are not justified.
understanding. Chemistry is by its very nature a fuzzy science, We present results of quantum chemical calculations mostly
because the jungle of boundless number of molecular structures using DFT methods, which are well suited for a bonding
and reactions request methodical schemes that serve as guidance analysis. The focus is not on high numerical accuracy but on the
for future directions of chemical research. The quantum nature of the interactions. On the other hand, the calculated
theoretical postulates are the physical framework for chemistry, observables of the molecules given in this work such as the
but the inner substance of chemistry is guided by models. equilibrium geometry and the bond dissociation energy are
Unlike the earlier heuristic models, which were based on assured to be in reasonable agreement with experiment, in
assumptions that are rooted in classical physics, modern accordance with condition 1 in Scheme 2.
bonding models come from well-defined though chemical- 7.1. H2+, H2, Li2+, Li2
intuition guided partitioning schemes of accurate quantum
chemical methods. They should fulfill the conditions that are Table 1 shows the calculated energy components for the
shown in Scheme 2. The advantage is that the comparison and interactions in H2+, H2, Li2+, and Li2 according to the EDA-
trend of different molecules can now be made with the help of
numbers rather than hand-waving arguments. The finding that Table 1. EDA-NOCV Results of H2, H2+, Li2, and Li2+ Species
different partitioning schemes may lead to different and at the RPBE/TZ2P//BP86/def2-TZVPP Levela
sometimes conflicting views should not be taken as argument Molecule H2 H2+ Li2 Li2+
against their use. Instead, the assumptions of a model and the +
Fragments [H] + [H] [H] + [H] [Li] + [Li] [Li]+ + [Li]
technical details of their implementation should be considered
before a conclusion is made. This requests the knowledge about ΔEint −106.6 −68.7 −20.8 −28.5
ΔEPauli 0.0 0.0 1.9 2.1
the most important aspects of the theoretical methods that are
ΔEelstatb 5.5 17.6 −8.3 (36.7%) 1.6
employed, just as is done with experimental spectroscopic
ΔEorbb −112.1 −86.3 −14.3 −32.2
methods. (100%) (100%) (63.3%) (100%)
The following conclusions arise from this section: ΔEorb(σ)c −111.5 −84.9 −12.9 −32.2
• In the quantum world, the physical reality of an electron is (99.5%) (98.4%) (90.2%) (100%)
a
not entirely assigned to its electronic charge distribution Energies are in kcal/mol. bThe values within the parentheses show
ρ, which represents only a projection onto a space of lower the contribution to the total attractive interactions ΔEelstat + ΔEorb.
information content; its completeness is only provided by For those cases where ΔEelstat is positive, it is excluded. cThe
remaining small contributions come from polarization functions.
its wave function Ψ. The wave function Ψ contains more
information about the behavior of the electron than ρ. In
chemistry, this comes to the fore for example in the NOCV method. The intrinsic interaction energy ΔEint is in these
outcome of pericyclic reactions, or in any spectroscopic cases identical to the bond dissociation energy De, because there
investigation, which can only be explained when the is no electronic or geometric relaxation of the fragments. The
symmetry and sign pattern of Ψ is considered. one-electron bond in H2+ has a bond energy of De = 68.5 kcal/
mol, which is nearly two-thirds of the bond strength in H2. The
• Models, in particular bonding models, are an integral part bonding in H2+ comes exclusively from the interference of the
of chemical research. Chemical research depends on the wave function, and the orbital interactions ΔEorb provide 100%
existence of bonding models, which provide an ordering of the attractive contribution to ΔEint. The electrostatic
scheme for the infinite number of molecules and interactions ΔEelstat at the equilibrium distance are repulsive. A
reactions. naı̈ve view might anticipate some Coulombic attraction of the
• The numerical outcome of modern partitioning schemes electron of the hydrogen atom by H+. This is misleading,
is not measurable quantities, but they are very useful tools because the electronic charge would be withdrawn from the
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vicinity of the nucleus toward the internuclear region. It can
easily be shown that the electrostatic attraction in the
internuclear region is weaker than in the core region, because
the distance to the nuclei becomes larger. The stabilization
comes from the lowering of the kinetic energy due to the
interference of the wave function.170,171 This is the physical
origin of ΔEorb.172
The second electron in H2 enhances the bond energy to a
smaller extent than the first electron in H2+. The electrostatic
interactions ΔEelstat at the equilibrium geometry of H2 are
repulsive, but only to a minor extent that does not significantly
influence the overall internal energy. They become weakly
attractive only at longer distances. The deformation densities,
which are associated with the bond formation in H2+ and H2, are
shown in Figure 4. The direction of the charge flow from the
Figure 4. Plot of deformation densities Δρ of H2, H2+, Li2, and Li2+
species at the RPBE/TZP//BP86/def2-TZVPP level. Energy values are
in kcal/mol. The direction of the charge flow is red → blue.
donating to the accepting areas has the color code red → blue. It
becomes obvious that there is a charge accumulation in H2 from
the hydrogen atoms to the interatomic region. The charge flow
in H2+ originating from the hydrogen atom ecompasses the
proton and the bonding area.
The bond formation of the valence isoelectronic species Li2+
and Li2 may superficially be expected to exhibit similar features,
but there are important differences between the valence
electrons of hydrogen and lithium. Below the 1s shell of
hydrogen there is the bare nucleus, whereas below the 2s shell of
lithium there is a polarizable 1s core. Charge flow of the valence
electrons of H during bond formation of H2 leaves the remaining
electronic charge under the Coulombic attraction of the nucleus,
which induces a rather large contraction of the 1s AO.173 In
contrast, the remaining 2s valence electrons of lithium in Li2
encounter Pauli repulsion by the 1s shell, which prevents
penetration toward the nucleus. This leads to significant
differences of the physical mechanisms of the bond formation
between the lithium and the hydrogen dimers. This becomes
obvious by inspection of the EDA-NOCV results in Table 1 and
the associated deformation densities in Figure 4.
The bond in Li2 is much weaker (De = 20.5 kcal/mol) than in
H2 (De = 112.9 kcal/mol). This can be mainly attributed to the
more diffuse 2s AO of lithium and the less weakly bonded 2s
electron in Li compared with the 1s electron in hydrogen. The
ionization energy (IE) of hydrogen atom is 13.60 eV whereas the
IE of Li is only 5.39 eV. This induces a significantly smaller
energy lowering through the interference of the wave
functions.173 The most surprising feature is the stronger one-
electron bond in Li2+ compared with the two-electron bond in
Li2. The rather soft singly occupied 2s AO of lithium becomes
strongly polarized by the positive charge and it mixes with the
2p(σ) orbital, which leads to enhanced interference of the
atomic wave functions compared with Li2. The deformation
density in Li2+ shown in Figure 4 nicely vizualizes the
polarization of the electronic charge upon bond formation.
This effect is so strong that the final energetic stabilization in Li2+
is stronger than in Li2. The second electron weakens particularly
the interference of the wave functions, because the interelec-
tronic interactions reduce the polarization, which effectively
weakens the bond. The results for H2+, H2, Li2+, and Li2 are
striking evidence that chemical bonding does not originate from
spin coupling of the electrons, which is often wrongly
stated.174−176
The following conclusions arise from this section:

Table 2. Energy Partitioning Analysis of the H−H, N−N, C−O, and B−F Bonds of Diatomics A−B at BP86/TZ2P+a
A−B H2 N2 CO BF
ΔEint −113.0 −240.2 −267.6 −186.0
ΔEPauli 0.0 802.2 582.7 484.4
ΔEelstatb +5.8 −312.8 (30.0%) −240.1 (28.2%) −214.0 (31.9%)
ΔEorbb −118.7 (100%) −729.6 (70.0%) −610.1 (71.8%) −456.4 (68.1%)
ΔEσc −118.7 (100%) −478.7 (65.6%) −310.6 (50.9%) −404.8 (88.7%)
ΔEπc 0.0 −250.9 (34.4%) −299.4 (49.1%) −51.8 (11.3%)
R(A−B)e 0.750 (0.741) 1.102 (1.098) 1.136 (1.128) 1.275 (1.262)
P(A−B) 1.0 3.03 2.30 0.86
μ⃗b,d 0 0 −0.19 (−0.11) −1.03
q(A) 0 0 +0.46 +0.54
De −111.6 −237.6 −265.6 −184.3
D0e −105.0 (−103.3) −234.2 (−225.0) −262.6 (−255.7 ± 1) −182.4 (179.9 ± 3)

a
The interacting fragments of N2, CO, and BF are shown in Figure 6. Energy values in kcal/mol, bond lengths R in Å, dipole moments μ⃗ in Debye.
NBO atomic partial charge q(A), and Wiberg bond order P(A−B). Bond dissociation energies De and ZPE corrected values D0. bThe values in
parentheses give the percentage contribution to the total attractive interactions ΔEelstat + ΔEorb. cThe values in parentheses give the percentage
contribution to the total orbital interactions ΔEorb. dA negative value indicates that the first atom of A−B is the negative end of the dipole moment.
e
Experimental values from ref 24 are given in parentheses.

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• The covalent bond in Li2 is much weaker than in H2,

because the less strongly bonded 2s electron of Li,
shielded by the 1s core electrons, is much more diffuse
than the 1s electron of H and encounters weaker
stabilization through interference.
• The one-electron bond in Li2+ is stronger than the two-
electron bond in Li2, because the induction enhances the
interference of the wave functions. This is striking
evidence that covalent bonding does not come from
electron pairing but from electron-sharing.
• The charge flow associated with the covalent bond
formation can nicely be visualized using the deformation
density from EDA-NOCV calculations.
7.2. H2, N2, CO, and BF
The isoelectronic molecules N2, CO, and BF are well suited to
discuss the results of a quantum chemical bonding analysis in
comparison with traditional bonding models. Table 2 shows the
numerical NBO and EDA-NOCV results of the three diatomic
species along with H2, which demonstrates the exceptional
features of dihydrogen. The chemical bond of H2 is the standard
model for introducing covalent bonding, because the occurrence
of bonding in terms of interfering wave functions can best be
studied by choosing the simplest example. The data in Table 2
also show the calculated and experimental bond lengths and
BDEs, which are in good agreement.
There are three major qualitative differences when one goes
from H2 to N2. One difference is the occurrence of Pauli
repulsion between electrons with the same spin. The very large
value of ΔEPauli = 802.2 kcal/mol in N2, which is the largest
absolute value of all energy components, demonstrates the
relevance of the Pauli repulsion for chemical bonding. The
second difference is the large attractive Coulombic attraction of
ΔEelstat = −312.8 kcal/mol, which contributes 30% to the total
interatomic attraction in N2. This comes from the overlap of the
electron density of one nitrogen atom with the nucleus of the
other nitrogen atom, which carries a much larger positive charge
than hydrogen. A systematic study of 224 homo- and
heterodiatomic molecules by Spackman and Maslen in 1986
showed that the quasiclassical Coulomb attraction in nearly all Figure 5. (a) Overlap integrals of the atomic 2s and 2p orbitals of N2 as
of them is quite strong.177 The rather weak electrostatic a function of the interatomic distance. (b) Calculated EDA values for
attraction in H2 at longer bond lengths, which becomes repulsive N2 as a function of the interatomic distance. The reference value re = 0.0
is the calculated equilibrium bond length 1.102 Å. Reprinted with
at equilibrium distances, comes from the small nuclear charge of permission from ref 28. Copyright 2006 John Wiley and Sons.
hydrogen. A mathematical explanation for this finding was given
by Kutzelnigg178 and later by Bickelhaupt and Baerends.131 The
third major difference concerns the occurrence of π bonding in distance and is rather found at a bond length that is ∼0.2 Å
N2, which is not surprising. The breakdown of the orbital shorter than the equilibrium value. The additional σ bonds
interactions ΔEorb suggests that two-thirds of the covalent should further shorten the bond. The explanation for the
bonding comes from σ orbitals and the remaining one-third equilibrium bond length, which is clearly longer than what one
from π orbitals. This agrees with the general understanding that would expect using the maximum overlap guideline, is given in
π bonds are weaker than σ bonds.179 Figure 5b. It shows the variation of the different energy
The relevance of Pauli repulsion for chemical bonding comes components as a function of the interatomic distance. All
clearly to the fore when the factors determining the equilibrium attractive components of ΔEint still become stronger when the
length of a chemical bond are considered. A popular explanation interatomic distance becomes shorter than the equilibrium
from the early days of quantum chemistry suggests that the bond value. It is the Pauli repulsion ΔEPauli which prevents further
length of a σ bond, re, is mainly determined by the maximum shortening of re below the equilibrium distance. It is only in H2 that
overlap of the orbitals. The bond becomes further shortened the equilibrium bond length is determined by the maximum
when there is an additional π bond, because the maximum overlap, because there is no Pauli repulsion in dihydrogen.180
overlap of a π orbital is at r = 0. This explanation is, however, not The electronic structure of CO exhibits peculiar features,
valid as the strong effect of Pauli repulsion is ignored. Figure 5a which can be explained with the help of the EDA-NOCV results.
shows the overlap of the σ and π orbitals of N2 at different CO has a stronger bond than N2; the BDE of CO (De = 265.6
interatomic distances r. It becomes obvious that the maximum kcal/mol) is larger than that for N2 (De = 237.6 kcal/mol). The
overlap of the σ orbitals is not yet reached at equilibrium inspection of the energy terms shows that the attractive
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Figure 6. Schematic representation of the most important Lewis structures of N2, CO, and BF and the electron configurations of the atoms which lead
to electron-sharing bonds A−B or dative bonds A→B. Reprinted with permission from ref 152. Copyright 2019 Springer Nature.

Figure 7. Contour line diagram showing the Laplacian ∇2ρ(r) of (a) CO and (b) BF at BP86/def2-TZVPP. Blue solid lines indicate areas of charge
depletion (∇2ρ(r) > 0), and red solid lines indicate areas of charge accumulation (∇2ρ(r) < 0). The bond critical point is shown in black. Solid lines
connecting the atomic nuclei are the bond paths, while the solid lines crossing the bond paths indicate the zero-flux lines which separate the donor and
acceptor moieties. The thick green arrow indicates the atomic dipole component at C in CO and B in BF. Reprinted with permission from ref 47.
Copyright 2006 John Wiley and Sons. .

components in CO, i.e., electrostatic attraction ΔEelstat and
orbital interaction ΔEorb, are both weaker than in N2. The
stronger bond in CO comes from the significantly weaker Pauli
repulsion ΔEPauli than in N2. The strength of ΔEPauli strongly
depends on the overlap of the orbitals, even more than ΔEorb
(see Figure 1).28 The overlap of the unequal σ AOs in CO is
smaller than the overlap of the equal σ AOs in N2, which leads to
weaker Pauli repulsion that even compensates for the weaker
Coulomb attraction in the former molecule.
The breakdown of ΔEorb of CO into the σ and π components
suggests that the latter contribution provides 49% of the orbital
interactions; that is, σ and π bonding have nearly the same
strength. This is in contrast to N2, where π bonding contributes
only 34% of ΔEorb. This can be explained with the different types
of covalent interactions in CO and N2. Figure 6 shows
schematically the interacting orbitals in the two molecules.
The σ and π bonds in N2 come from electron-sharing
interactions between the nitrogen atoms in the 4S ground
state. In contrast, the interactions between carbon and oxygen in
the 3P ground states lead to a dative σ bond C←O and two
electron-sharing π bonds CO, which agrees with the original
description suggested by Sidgwick.46 Since dative bonds
are always weaker than electron-sharing bonds between the
same atoms (see the section below), the percentage contribution
of π bonding in CO is higher than in N2. At the same time, the
bond order of CO becomes smaller (2.30) than that in N2
(3.03), because the overlap of the uneven orbitals is smaller than
those of even orbitals. The answer to the question concerning
the multiple bond character of a bond depends on the criterion
8798
which one has in mind; this may be the overlap population or the
energetic stabilization of the σ and π bonds.
There is a third property of CO that has puzzled chemists for
some time and which has led to controversies: The dipole
moment of CO is rather small and has its negative end at the less
electronegative carbon atom (−0.11 D).181 A simple consid-
eration in terms of electronegativities would suggest a sizable
dipole moment with the negative end at oxygen. The calculation
of the atomic partial charges with the NBO method gives indeed
a negative charge at oxygen and a positive charge at carbon
(Table 2). The apparent contradiction is easily resolved when
one recalls that dipole moments are vector properties whereas
partial charges are scalar properties. The crucial quantity here is
the topography of the charge distribution. This becomes obvious
by inspection of the Laplacian distribution ∇2ρ(r) of CO, which
is shown in Figure 7a. The electronic charge in the internuclear
region is clearly polarized toward the more electronegative
oxygen atom. This gives a bond charge component to the dipole
moment that is directed toward oxygen. The key components
are the charges around the nuclei. The charge concentration
around the oxygen nucleus is spherically symmetric, but the
charge concentration around the carbon atom has a local center
of charge concentration, which is rather far away from the
nucleus. This is indicated by the green arrow. This local charge
can be associated with the lone-pair electrons at carbon, which
strongly influence the chemical reactivity of CO. The aspherical
charge distribution at carbon introduces a large dipole
component toward the carbon end, which overcompensates
the effect of the polarity on the dipole moment. A breakdown of
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the total dipole moment into individual orbital components

showed that all valence orbitals have a dipole component C → O
except the HOMO (Highest Occupied Molecular Orbital),
which has a large component in the opposite direction C←O
that overcompensates the former (Table 3).47 The unexpected
direction of the dipole moment of CO comes from the
topography of the charge distribution.

Table 3. Orbital Components to the Total Dipole Moment of

CO at BP86/6-311++G(3df, 3pd)a
Orbital Bond Moment
MO 1 σ 4. 67
MO 2 σ −6. 23
MO 3 σ 1. 57
MO 4 σ 4. 52
MO 5 π 1. 75
MO 6 π 1. 75
MO 7 σ (HOMO) −8. 21
∑ −0.18 (exp. −0.11)
a
Values in Debye. Negative values indicate that the negative end is at
the carbon atom. The origin of the CO12+ ion is chosen at the position
where the dipole moment of the nuclei becomes zero. The orbital
components were calculated with nuclear charges which are scaled by
6/7 (carbon) and 8/7 (oxygen). This leads to orbital components of
the dipole which after summation give the total dipole moment of the
neutral molecule, which is origin independent. The data are taken
from ref 47. Figure 8. MO correlation diagram of the 2s and 2p AOs of first octal-
row atoms. Reprinted with permission from ref 28. Copyright 2006
Table 2 shows that the BDE of BF is much smaller (De = 184.3 John Wiley and Sons.
kcal/mol) than that of isoelectronic N2 and CO. All three energy
terms of the EDA-NOCV are weaker in BF than in N2 and CO, and Pauli repulsion, but not by the maximum orbital
and therefore, they do not explain the overall reason for the bond overlap.
weakening. A possible rationalization of the bond weakening • CO has a triple bond, which consists of a dative σ bond
comes from the strength of the σ and π bonds in BF. The and two electron-sharing π bonds . The stronger
absolute and relative contribution of π bonding in BF is much bond in CO than in N2 can be explained with the weaker
smaller than in the other isoelectronic dimers. Inspection of the Pauli repulsion in carbon monoxide.
interacting orbitals explains the finding. Figure 6 shows that the
π interactions in BF come from dative bonding from the • BF has an electron-sharing B−F σ bond, which is
very electronegative fluorine atom to the electropositive boron, supported by two relatively weak dative π bonds .
whereas the σ bond is due to electron-sharing interactions in B− The weak π bonds explain why BF is more weakly bonded
F. Since the former provide only 11% to the covalent bond, it than N2 and CO.
seems reasonable to describe the molecule with a Lewis • The dipole moments of CO (−0.11 D) and BF (−1.03
structure that has only a single bond. The nature of the σ and D), which have their negative ends at the respectively
π bonding components in BF are the opposite of CO. more electropositive atoms C and B, are due to the
The electronic structure of BF nicely supports the above anisotropic charge distribution in the molecules. The σ
explanation for the dipole moment in CO. The Laplacian lone-pair electrons induce a local vector component,
distribution ∇2ρ(r) of BF shown in Figure 7b shows that the which leads to the surprising direction of the dipole
charge distribution in the bonding region is even more polarized moments.
toward fluorine due to the larger difference in electronegativities 7.3. First Octal-Row Sweep Li2−F2 and Related Molecules
compared to CO. However, the local charge concentration at
The physical nature of the chemical bond can be best
boron in BF has a larger distance from the nucleus than the
understood by analyzing the interatomic interactions in
charge concentration at carbon in CO, because the lone-pair
diatomic molecules. Polyatomic molecules introduce a plethora
orbital at boron is more diffuse than the carbon lone-pair in CO.
of variations, which are the infinite playground of chemistry, but
As a result, the total dipole moment of BF is even larger (−1.03
they can significantly change the essential features of chemical
D) than that of CO with the negative end at boron.
bonding. Particular classes of compounds, which exhibit specific
The following conclusions arise from this section:
types of chemical bonds such as clusters and aromatic systems,
• The appearance of valence electrons that possess the same are discussed in other articles of this thematic issue. We focus
spin introduces strong Pauli repulsion in N2, which is mainly on diatomic molecules and we extend our above
missing in H2. presented studies to a systematic first-row sweep of Li2−F2,
• The equilibrium bond lengths in molecules that have where we try to connect classical bonding models with a
more than two electrons is determined by the equilibrium quantum chemical analysis. We also discuss recent theoretical
between Coulombic forces, attractive orbital interactions, studies of low-valent main-group compounds, which possess
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Table 4. Energy Partitioning Analysis of the First Row Dimers E2 (E = Li−F) in C2v at BP86/TZ2Pa
E Li Be B C N O F
el. State 1
Σg+ 1
Σg+ 3
Σg − 1
Σg+ 1
Σg+ 3
Σg− 1
Σg+
ΔEint −20.7 −7.9 −74.7 −140.8 −240.2 −141.9 −52.9
ΔEPauli 1.8 41.6 135.0 252.2 802.4 464.9 146.1
ΔEelstatb −8.3 (36.9%) −17.9 (36.1%) −33.1 (15.8%) −3.2 (0.8%) −312.9 (30.0%) −159.7 (26.3%) −41.0 (20.7%)
ΔEorbb −14.2 (63.1%) −31.6 (63.9%) −176.5 (84.2%) −389.8 (99.2%) −729.8 (70.0%) −447.1 (73.7%) −157.8 (79.3%)
ΔΕ(σ)c −14.2 −31.6 −104.5 (59.2%) −201.7 (51.8%) −478.8 (65.6%) −319.5 (71.5%) −151.5 (96.0%)
ΔΕ(π)c 0.00 0.00 −72.0 (40.8%) −188.0 (48.2%) −251.0 (34.4%) −127.6 (28.5%) −6.2 (4.0%)
ΔEcorr.f 0.3 0.00 1.9 3.3 4.2 4.8 2.7
De d 20.4 (24.6) 7.9 (2.2; 2.7[calc.])e 72.8 (71.2) 137.5 (145.9) 236.1 (228.4) 137.1 (120.2) 50.2 (38.3)
E−Ed 2.731 (2.673) 2.442 (2.45)e 1.617 (1.590) 1.253 (1.243) 1.102 (1.098) 1.224 (1.208) 1.420 (1.412)
a
Energies in kcal/mol, distances E−E in Å. Values are taken from ref 28. bValues in parentheses give the percentage contribution to the total
attractive interactions ΔEelstat + ΔEorb. cValues in parentheses give the percentage contribution to the total orbital interactions ΔEorb. dExperimental
values in parentheses from ref 24, unless otherwise specified. eExperimental value for De and E−E; Bondybey, V. E. Chem. Phys. Lett. 1984, 109,
436; calculated value for De; Martin, J. M. L. Chem. Phys. Lett. 1999, 303, 399. fCorrection for the spin polarization.

Figure 9. Schematic representation of the electron configuration and the orientation of the atoms with the chosen orbital populations for the EDA.
Note that for the 3Σg− states of Si2, O2, and S2 a spin change of one electron in a singly occupied p(π) orbital takes place in the EDA calculation.
Reprinted with permission from ref 28. Copyright 2006 John Wiley and Sons.

chemical bonds that can be understood by using the undistorted
E2 fragments as reference.
Figure 8 shows a correlation diagram of the (n)s(n)p valence
AOs of main-group atoms of the first octal row Li−F with the
MOs of the diatomic molecules. The shape and the splitting of
the MOs consider the energy levels of the AOs and the
symmetry-allowed mixing (hybridization) of the orbitals. The
hybridization lowers the energy level of the bonding 2σg+ MO
and raises the energy of the bonding 3σg+ MO, which for some
8800
elements becomes slightly higher in energy than the 1πu MO.
This explains why B2 has a X3Σg− ground state and C2 has a
X1Σg+ ground state.24 The hybridization lowers the antibonding
character of the 2σu+ MO and raises the antibonding strength of
the 3σu+ MO. Thus, the strengths of the bonding 2σg+ MO and
antibonding 2σu+ MO do not fully cancel. However, the energy
difference between the 3σg+ MO and the 1πu MO is very small
and the ordering depends on the nature of the atoms. The
analogous valence 4σg+ MO and 2πu MO of Si2 exhibit a reverse
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order; that is, the 4σg+ is below the 2πu. Thus, the ground state of
Si2 is the X3Σg− triplet state. On the other hand, Al2 has the same
X3Σg− ground state as B2.24
7.3.1. Li2, Be2 and Related Molecules. The MO diagram
in Figure 8 and the aufbau principle are a useful starting point for
the discussion of chemical bonds in diatomic molecules Li2−F2.
But they are not sufficient for understanding all features of the
bonds, as was shown above for the comparison of Li2 with Li2+. It
must be complemented by a quantum chemical analysis, which
considers all types of interatomic interactions. Table 4 gives the
results of EDA calculations of Li2−F2.28 The comparison of the
calculated bond lengths and bond dissociation energies shows
the same trends, which makes the data a reasonbale fundament
for the bonding analysis. It is important to consider the
geometrical arrangement of the atomic configurations for the
interatomic interactions, which are shown in Figure 9, in order
to understand the calculated numbers. The construction of the
AO arrangements corresponds to the MO correlation diagram.
The EDA results for Li2 were already given in Table 1, albeit
with a different DFT functional. A comparison with the numbers
in Table 4 shows that the results change very little when a
different functional is used. The EDA values for Be2 suggest very
weak bonding, which is due to the strong Pauli repulsion
compensating most of the electrostatic attraction and covalent
contribution. The net attration of ΔEa1(σ) = −31.6 kcal/mol in
Be2 reveals that the hybridization in the bonding 2σg+ MO and
antibonding 2σu+ MO yields a net stabilization, which is
annihilated by the Pauli repulsion. The naı̈ve view of a bond
order of zero for Be2 is only supported when the Pauli repulsion Figure 10. Shape and eigenvalues of the lowest unoccupied Hartree−
is considered. Fock MO (LUMO) and the relevant occupied valence orbitals of Be2F2
using a cc-pVTZ basis set.182 Reprinted with permission from ref 182.
Inspection of the occupied valence MOs in Be2 gives a hint Copyright 2016 John Wiley and Sons.
toward attempts to stabilize molecules that posssess a Be−Be
bond. Substituents which withdraw electronic charge from the
antibonding 2σu+ MO but donate electronic charge into the repulsion in B2 (X3Σg−) comes only from electrons in the σ
bonding 2σg+ MO should enhance the Be−Be bond. This is space, the total σ interactions, i.e., attraction due to interference
indeed achieved in Be2F2, which has a theoretically predicted of the wave functions (ΔEorb) plus repulsion due to spatial
bond dissociation energy of D0298 = 65.0 kcal/mol at the exclusion of electrons with the same spin (ΔEPauli), become
CCSD(T)/cc-VTZ level of theory.182 Figure 10 shows the destabilizing. The simple bonding model of the MO correlation
valence MOs of the molecule. The antibonding inner lobes of Be diagram in terms of only π bonding in B2 is thus supported when
in the HOMO−4 have nearly completely disappeared whereas the Pauli repulsion is considered.
the HOMO is a bonding orbital. This explains the surprisingly The analysis of the orbital interactions in B2 was the starting
large strength of the Be−Be bond in Be2F2, which is also point for the eventually successful synthesis of a molecule with a
predicted to be thermodynamically stable relative to Be + BeF2 genuine BB triple bond. Calculations of group-13 complexes
in the gas phase. The isolation of Be2F2 in a bulk is energetically NHCMe→E2←NHCMe (NHCMe = N-heterocyclic carbene with
unfavorable, because the large atomization energy of beryllium methyl groups at nitrogen) with E = B, Al, Ga, In predicted that
from the metal (ΔHf = 77.4 kcal/mol)183 and the heat of the boron species B2(NHCMe)2 has a linear coordinated
sublimation of BeF2 (ΔHsub = 55.6 kcal/mol)184 make it unlikely geometry with a very short B−B distance.185 A bonding analysis
that pure beryllium subfluoride can be prepared. But Be2F2 suggested that the B2 species in B2(NHCMe)2 is in the
should be a stable molecule in the gas phase, and it may also be electronically excited (3)1Σg+ reference state, which has two
isolated in an inert matrix.182 vacant σ MOs with suitable symmetry that may serve as acceptor
7.3.2. B2 and Related Molecules. According to the simple orbitals for donor−acceptor interactions with the NHCMe
MO correlation diagram, most of the covalent bonding in the ligands (Figure 11). The energy calculations predicted that
X3Σg− ground state of B2 comes from π bonding, because the B2(NHCMe)2 is thermodynamically stable with regard to
contributions from the bonding 2σg+ MO and antibonding 2σu+ dissociation into B2 in the electronic X3Σg− ground state and
MO cancel to some extent. The EDA calculation of B2 suggests two NHCMe ligands by >180 kcal/mol. The bond strength of the
that the overall bonding comes mainly from the ΔEorb term, intrinsic interactions NHCMe→E2←NHCMe clearly compen-
which comprises 60% σ bonding and 40% π bonding. The π sates for the excitation energy of B2 for the process X3Σg−→
interactions come from the two singly occupied degenerate π (3)1Σg+, which amounts to 106.4 kcal/mol.
orbitals. Thus, the hybridization of the bonding 2σg+ MO and The theoretically predicted stability of B2(NHCMe)2 was
antibonding 2σu+ MO in B2 is very effective and leads to a verified by the synthesis and X-ray structural characterization of
predominantly σ bonded species, if only the stabilizing orbital B 2 (NHC R ) 2 carrying bulky groups R at nitrogen by
interactions are considered. A different interpretation arises Braunschweig and co-workers.186,187 The experimental value
when the Pauli repulsion is taken into account. Since Pauli for the B−B distance of 1.45 Å was in very good agreement with
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Figure 11. Schematic diagram of the valence orbitals and orbital occupation of B2 in (a) the X3Σg− ground state and (b) (3)1Σg+ excited state. (c)
Schematic representation of the charge donation from the out-of-phase (+,−) and in-phase (+,+) combinations of the ligand lone-pair σ orbitals into
the vacant orbitals of B2 in the 1Σg+ excited state. (d) Calculated energies of the excitation energy of B2 from the ground state to the reference state and
bond dissociation energy De of B2(NHCMe)2 at BP86/def2-TZVPP.189 Reprinted with permission from ref 189. Copyright 2015 Royal Society of
Chemistry.

the calculated data of 1.47 Å for the model compound. But the
notation of a genuine BB triple bond in B2(NHCR)2 was
challenged on the basis of experimental results, where the
boron−boron distance in OBBO was taken as reference for a
single bond.188 This led to a detailed bonding analysis of
B2(NHCMe)2 with the EDA-NOCV method, which convinc-
ingly demonstrated that the molecules B2(NHCR)2 have a
boron−boron triple bond.189 It was shown that there is a
significant π-bonding contribution in the boron−boron bond of
OBBO which makes it unsuitable as reference for a single bond.
Table 5 gives the numerical EDA-NOCV results for
B2(NHCMe)2. Figure 12 displays the deformation densities of
the four most important pairwise orbital interactions Δρ1−4
along with the interacting orbitals of the fragments and the
resulting MOs of the complex. The combined pictures provide
8802
detailed insight into the change of the electronic structure of the
fragments that comes from the formation of the bonds. The
strongest interaction ΔEσ1 (−112.7 kcal/mol) comes from the
in-phase (+,+) NHCMe→B2← NHCMe σ-donation into the
LUMO+1 of (3)1Σg+ B2 while the contribution of the out-of-
phase (+,−) donation ΔEσ2 (−86.9 kcal/mol) into the lower-
lying LUMO (Lowest Unoccupied Molecular Orbital) is a bit
weaker due to the better overlap of the former (+,+) donation.
The other two contributions ΔEπ1 and ΔEπ2 arise from
NHCMe←B2→NHCMe π-backdonation, which is smaller than
the σ-donation. They are not degenerate, because the planes of
the NHC ligands are in a twisted conformation.
The shape of the deformation densities shows not only the
formation of the boron−ligand bonds but also the alteration of
the boron−boron bond. The shapes of Δρ1 and Δρ2 and the
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Table 5. Results of the EDA-NOCV calculations for NHCMe amino carbene) ligand enhances the π backdonation to the
→ B2 ← NHCMe at BP86/TZ2P Using the Fragments ligand, which leads to a longer B−B and shorter B-L
B2[(3)1Σg+] and (NHCMe)2 as Interacting Speciesa bonds.190,191
We point out that the compound B2(NHCR)2 that was
B2(NHCMe)2
isolated by Braunschweig in 2012 was not the first L→B2←L
Interacting fragments B2[(3) Σg+] and (NHCMe)2
1
species experimentally observed. Zhou and co-workers reported
ΔEint −307.5 in 2002 the synthesis of the dicarbonyl complex B2(CO)2 in a
ΔEPauli 259.0 low-temperature argon matrix.192 The experimental and
ΔEelstatb −252.3 (44.5%) theoretical vibrational spectra suggest that the molecule has a
ΔEorbb −314.2 (55.5%) linear structure. The authors proposed that B2(CO)2 exhibits
ΔEσ1 L→(B2)←L (+,+) donationc −112.7 (35.9%) some boron−boron triple bond character, and they suggested
ΔEσ2 L→(B2)←L (+,-) donationc −86.9 (27.7%) that the molecule should be drawn as OCBBCO. A
ΔEπ1 L←(B2)→L π backdonationc −48.0 (15.3%) similar conclusion was drawn by Li and co-workers, who
ΔEπ2 L←(B2)→L π′ backdonationc −42.4 (13.5%)
observed the boron compound [B2(BO)2]− in the gas phase
ΔErest −24.2 (7.7%)
using photoelectron spectroscopy.193 The authors reported
q(B2) −0.36
a
quantum chemical calculations of the series [B2(BO)2]0,−,2−,
All energy values in kcal/mol. Calculated NBO partial charge of B2 in with the dianion being isoelectronic with B2(CO)2. Subsequent
e. bThe value in parentheses gives the percentage contribution to the
theoretical studies of B2L2 with various ligands supported the
total attractive interactions ΔEelstat + ΔEorb. cThe value in parentheses
gives the percentage contribution to the total orbital interactions description of the bonding situation in terms of dative bonds
ΔEorb. L→B2←L. EDA calculations of B2(CO)2 showed substantial π
backdonation OC←B2→CO, which are nearly as strong as the σ
associated σ orbitals HOMO−6 and HOMO−13 of the donation OC→B2← CO.194
complex (Figure 12a, b) suggest that the NHCMe →B Table 6 shows the EDA results of B2L2 species with
interactions concurrently exert an opposite effect on the isoelectronic ligands L = CO, N2, BO−, not only for the dative
boron−boron bonding. The HOMO−6 is bonding and bonds between the ligands and B2 but also for the boron−boron
HOMO−13 is antibonding with respect to the B−B bonds. bonds. It becomes obvious that all bonds have a significant
Thus, the effect of the σ interactions NHCMe→B2←NHCMe on triple-bond character, which let the authors propose that the
the B−B σ bond partially cancel each other. In contrast, the LBBL systems are molecules with all-triple bonds.
effect of the π backdonation NHCMe←B2→NHCMe clearly 7.3.3. C2 and Related Molecules. The EDA results for the
weakens the B−B bond, which becomes visible by inspection of X1Σg+ ground state of C2 suggest that the attractive σ and π
Δρ3 and Δρ4 (Figure 12c, d). This has been utilized to fine-tune orbital interactions have nearly the same strength (Table 4). The
the B−B bond by variation of the π-acceptor strength of ligands attraction by the σ orbitals is compensated by the Pauli repulsion
L in L→B2← L. Replacement of the unsaturated NHC ligand by of the doubly occupied σ MOs, which leaves the π contribution
the saturated homologue NHCsat or the CAAC (cyclic alkyl as the sole component of the stabilizing orbital interactions. But

Figure 12. Plot of the interacting donor and acceptor orbitals and calculated eigenvalues ε of (NHCMe)2 and (1Σg+) B2 (right two columns) and
matching MOs of the complex NHCMe→BB←NHCMe (second column from the left). Plot of the deformation densities Δρ with connected
stabilization energies ΔE of the four most important orbital interactions in B2(NHCMe)2 which indicate the associated charge flow red → blue.189
Reprinted with permission from ref 189. Copyright 2015 Royal Society of Chemistry.

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Table 6. EDA Results of LBBL at the BP86/TZ2P Levelba

OCBBCO N2BBN2 [OBBBBO]2− OCBBCO N2BBN2 [OBBBBO]2−
4 − 4 − − 4 −
Interacting 2 BCO ( Σ ) 2 BNN ( Σ ) 2 [BBO] ( Σ ) B2 [(3) Σg ] + 2 CO ( Σ )
1 + 1 +
B2 [(3) Σg ] + 2 N2 ( Σg )
1 + 1 +
B2 [(3)1Σg+] + 2 BO− (1Σ+)
fragments
ΔEint −155.2 −155.3 −89.7 −267.7 −223.1 −326.1
ΔEPauli 103.9 93.6 144.9 203.6 221.3 195.0
ΔEelstatc −108.7 −97.4 (39.1%) −71.0 (30.2%) −119.1 (25.3%) −94.5 (21.3%) −209.0 (40.1%)
(42.0%)
ΔEorbc −150.4 −151.5 −163.6 (69.8%) −352.2 (74.7%) −349.9 (78.7%) −312.2 (59.9%)
(58.0%) (60.9%)
ΔEσd −92.1 (61.2%) −91.3 (60.3%) −102.2 (62.5%) −193.7 (55.0%) −168.3 (48.1%) −233.1 (74.7%)
ΔEπd −58.3 (38.8%) −60.2 (39.7%) −61.4 (37.5%) −158.5 (45.0%) −181.6 (51.9%) −79.1 (25.3%)
ΔEprep 5.5 10.2 6.7 6.1 (112.4)e 9.8 (123.1)e 7.6 (180.7)e
ΔE(=-De) 149.7 145.1 83.0 261.6 (155.3)e 213.3 (107.0)e 318.5 (145.4)e
a
Values are taken from ref 194. bEnergy values in kcal/mol. cThe percentage values in parentheses give the contribution to total attractive
interactions ΔEorb + ΔEelstat. dThe percentage values in parentheses give the contribution to total orbital interactions ΔEorb. eEnergy with respect to
B2 (X3Σ g−) ground state.

Figure 13. Coefficients and weights of the four most important electron configurations a−d in the full-valence CAS(8/8)SCF/cc-pVTZ calculation of
(X1Σg+) C2.195 Reprinted with permission from ref 195. Copyright 2016 John Wiley and Sons.

the bonding in C2 is not well described with only one
configuration, because the occupied 1πu MO and the vacant
3σg+ MO are close in energy, which requests a multiconfigura-
tional calculation of C2 in order to reliably account for the
bonding situation. A (8/8) CASSCF (Complete Active Space)
calculation, where the 8 valence electrons occupy the complete
space of the 2s2p valence orbitals of C2, showed that the leading
configuration (2σg+)2(2σu+)2(1πu)2(1πu′)2(3σg+)0(1πg)0 (Fig-
ure 13a) has a weight of 71% of the total wave function.195 The
next important configuration, where only bonding σ and π MOs
are occupied, contributes 13.6% to the wave function (Figure
13b). The remaining configurations are less important. The
formal bond order of 2, which comes from the π bonds in the
leading configuration, becomes slightly higher by the second
important configuration that has a formal bond order of 4.
The nature and strength of the bond in C2 has been a topic of
an intensive and controversial debate in recent years, following
the suggestion by Shaik and co-workers that dicarbon has a
quadruple bond comprising two σ and two π bonds.196−199 The
assignment of a quadruple bond in C2 came from an analysis of
VB calculations. Several groups, who employed various MO and
VB methods, questioned in subsequent studies the suggestion of
a quadruple bond in C2.200−205 Calculations of bond orders
using different approaches gave values between 2−4, and thus,
they were not at all conclusive. The situation became
substantiated when Shaik et al. quantified the strength of the
intrinsic σ interactions in C2 and triply bonded acetylene HC
8804
CH. According to their VB calculations, the strength of the σ
interactions in C2 is 156.6 kcal/mol while σ bonding in acetylene
amounts to 138.7 kcal/mol.206−208
Following the reasoning of Shaik et al., the carbon−carbon
triple bond in HCCH stays essentially intact when the
hydrogen atoms are removed and the remaining unpaired
electrons couple with their inward lobe, which leads to a second
σ bond that is weaker than the first one but strong enough to
establish a fourth bond. The alternative view, which is based on a
CASSCF wave function, identifies a significant change in the σ
space of the remaining C2 fragment of acetylene after removing
the hydrogen atoms.195 The σ interactions comprise indeed two
rather than one component, but they are degenerate and very
weak. The overall σ interactions in C2 are much weaker than in
acetylene and the bonding situation may be described like a Be2
species that is held together by a “π-clip”.209
Table 7 shows some relevant properties of C2 and HCCH
for comparison. The carbon−carbon bond in C2 is longer and
has a smaller force constant and lower vibrational frequency than
in acetylene. Dicarbon has also a significantly lower bond
dissociation energy (BDE). The BDE may be questioned as a
measure of the bond strength, because the electronic reference
state of the dissociated fragments is not the same as in the
molecule. However, Figure 14 shows that the energy curve for
variation of the C−C distance in HnCCHn (n = 0−3) places C2
between ethylene and acetylene. Thus, all observable quantities
suggest that the carbon−carbon bond in C2 is weaker than in
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Table 7. Calculated Properties of C2 and HCCHa
C2 HCCH
Re(C−C) [Å] 1.256 1.216
kCC [mdyn/Å] 11.9 15.8
υCC [cm−1] 1837 1995
De(C−C) [kcal/mol] 144.0 228.2
a
Equilibrium distance Re(C−C), force constant kcc, vibrational
frequencies υCC, and bond dissociation energy De. Values are taken
from refs 195 and 200.
HCCH. A recent theoretical study of the 13C isotropic
magnetic shieldings came to the conclusion that the bond in C2
has a higher multiplicity but it is weaker than in HCCH.210
The suggestion that C2 has a quadruple bond that is stronger
than the carbon−carbon triple bond in acetylene appears
therefore questionable in the light of the properties of the two
molecules.
The stabilization of C2 with two donor ligands in compounds
C2L2 analogous to B2L2 has been a topic of theoretical and
experimental studies. The PPh3 bound derivative has been
generated at −78 °C but was reported to be unstable at
temperatures above −40 °C.211 Theoretical studies suggest that
the stabilization by NHC ligands is stronger than that by
phosphanes and that compounds C2(NHCR) might be stable at
room temperature.212 Deprotonation of the dication [(C2H2)-
(NHCR)]2+ with strong bases failed and gave the reduced
product instead.213 But the use of the CAAC ligand instead
Figure 14. (a) Calculated stretching force constants kCC at the full-valence CASSCF/cc-pVTZ level of HnCCHn (n = 3−0). (b) Potential energy curves
at CASSCF/cc-pVTZ for changing the C−C distances of HnCCHn (n = 3−0) from the equilibrium distance by ±0.15 Å in steps of 0.01 Å.195
Reprinted with permission from ref 195. Copyright 2016 John Wiley and Sons.
8805
Review
finally led to the isolation of the compounds C2(CAACR)2 with
different substituents R by two groups.214,215 The X-ray
structure analysis showed that the molecule slightly deviates
from a linear arrangement of the ligands along the central C2 axis.
The compounds may thus either be described as cumulene
CAACCCCAAC or as complexes CAAC→CC←
CAAC. EDA-NOCV calculations were carried out with the
fragments C2 and (CAAC)2 in the electronic singlet states for
dative bonding and quintet states for electron-sharing bonding
in the cumulene. Figure 15 shows schematically the electronic
reference states of C2. The (2)1Δg state, which has two vacant σ
orbitals, is the reference state for dative bonding L→CC←L
while the 5Δg state with four unpaired electrons in two σ and two
π orbitals is the reference state for electron-sharing double
bonding.216 As mentioned in the section above about the EDA-
NOCV method, the absolute values of the ΔEorb term indicate
the more favorable description of the bonding situation.
Calculations were also carried out for C2(CAACMe)2 and for
the related molecule C2(NHCMe)2. The numerical results of the
calculations are shown in Table 8.217
The data in Table 8 suggest that the bonding situation in
C2(NHCMe)2 may be reasonably well described with either
bonding model. The ΔEorb value for dative interactions (−686.0
kcal/mol) is only slightly smaller than the data for electron-
sharing double bonding (−707.9 kcal/mol). In contrast, the
ΔEorb value for dative interactions in C2(CAACMe)2 is much
larger (−720.5 kcal/mol) than that for electron-sharing double
bonding (−601.9 kcal/mol). This implies that the latter
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16. Note that the deformation densities and the associated

energies are the sum of the unequal contributions of the α and β
electrons in opposite directions, with the differences between
them being less important for the present work. Figure 16 shows
only the net deformation densities and the sum of the strength of
the orbital interactions.
The two strongest orbital interactions ΔEσ(+,+) and ΔEσ(+,−)
come from the (+,+) in-phase and (+,−) out-of-phase
combinations of the singly occupied σ orbitals, which lead to
charge accumulation (blue) in the C−C bonding region
between the (CAAC)2 and C2 fragments. The two σ
contributions have similar strength. In contrast, the π
contribution, ΔEπ(+,−), is much larger than ΔEπ(+,+). This is
because the former interaction releases the antibonding π
interaction of the central C2 fragment and introduces π bonding
between C2 and the CAAC ligands, whereas the latter weakens
Figure 15. Schematic diagram of the electronic reference states of C2 the π bonding in the C2 fragment. Note that the energy levels of
for dative bonding and electron-sharing bonding in C2L2. (a) (2)1Δg the interacting singly occupied orbitals related to Δρ3 are much
state; (b) 5Δg state. closer than the SOMOs that are associated to Δρ4.
7.3.4. N2 and Related Molecules. The chemical bond in
Table 8. EDA-NOCV Results at BP86/TZ2P of the Donor− N2 has been discussed in the above section 7.2. Dinitrogen is a
Acceptor and Electron-Sharing Interactions in C2(NHCMe)2 prototype for an electron-sharing triple bond, which consists of a
and C2(CAACMe)2 Using Singlet (S) and Quintet (Q) σ and two degenerate π bonds. The EDA results in Table 4
Fragmentsa suggest that two-thirds of the covalent interactions come from σ
C2(NHCMe)2 C2(CAACMe)2 bonding while one-third is due to π bonding, which nicely agrees
C2 (S) C2 (Q) C2 (S) C2 (Q)
with chemical intuition. Dinitrogen is considered a weak donor
ligand, which usually binds in complexes in the X1Σg+ electronic
Molecule (NHCMe)2 (NHCMe)2 (CAACMe)2 (CAACMe)2 ground state through its σ lone-pair orbitals in an end-on
Fragments (S) (Q) (S) (Q)
fashion.219 The electronic excitation energies of N2 are rather
ΔEint −647.8 −485.8 −712.0 −486.7
high, and thermochemical reactions of N2 normally involve only
ΔEPauli 361.5 622.5 344.0 480.2
the electronic ground state. Dinitrogen as acceptor species was
ΔEelstatb −323.4 −400.5 −335.5 −347.0
(32.0%) (36.1%) (31.8%) (36.6% virtually unknown until recently.
ΔEorbb −686.0 −707.9 −720.5 −601.9 One decade ago, a series of complexes L→E2←L where E2 are
(68.0%) (63.9%) (68.2%) (63.4%) diatomic main-group compounds of groups 14 and 15 stabilized
ΔE1 L-C2-L σ −205.1 −228.0 −220.8 −185.3 by NHC ligands L were isolated and structurally characterized
bonding (+,+)c (29.9%) (32.2%) (30.6%) (30.8%) by X-ray crystallography.220−223 The starting point was the
ΔE2 L-C2-L σ −192.5 −164.5 −191.3 −163.6 synthesis of Si2(NHCR)2 by Robinson in 2008,224 which was
bonding (+,-)c (28.1%) (23.2%) (26.4%) (27.2%)
ΔE3 L-C2-L π*- −200.2 −148.1 −213.2 −146.7
followed by the germanium and tin homologues
bondingc,d (29.2%) (20.9%) (29.6%) (24.4%) Ge2(NHCR)2225 and Sn2(NHCR)2226 in 2009 and 2012. The
ΔE4 L-C2-L π- −42.5 −102.0 −50.7 −52.1 group-15 adducts P2(NHCR)2 and As2(NHCR)2 were isolated in
bondingc,d (6.2%) (14.4%) (7.0%) (8.7%) 2008 and 2010.227,228 A theoretical paper by Wilson and co-
ΔErestc −45.7 −65.3 −44.5 −54.2 workers reported in 2012 the calculated bond dissociation
(6.6%) (9.3%) (6.4%) (8.9%)
a
energies of the group-14 and group-15 complexes E2(L)2 with L
All energies in kcal/mol.217. bThe value in parentheses gives the = NHC, PPh3, which showed that the group-15 adducts are
percentage contribution to the total attractive interactions ΔEelstat + clearly less stable than the group-14 homologues.212 Most
ΔEorb. cThe value in parentheses gives the percentage contribution to
the total orbital interactions ΔEorb. dThe notation π and π* refer to
species should in principle be isolable, except for the dinitrogen
the π MO of the C2 fragment. complexes N2L2, which were calculated to be thermodynami-
cally unstable toward dissociation of the ligands (Table 9,
numbers in bold).
molecule is best described as cumulene CAACCC Inspection of the experimental literature reveals surprising
CAAC, which agrees with the finding that the singlet−triplet findings. The compounds N2(NHCR)2 and N2(PPh3)2 had
split of the CAAC carbene is significantly smaller than that for earlier been reported as stable species that can easily be
NHC.218 The values of ΔEorb in Table 8 are marked in red to prepared.229,230 The experimental study of the synthesis and
highlight the particular relevance of the orbital term, which gives properties of N2(PPh3)2 was in conflict with the theoretical
the best description of the type of orbital interaction. result that the molecule is unstable toward loss of the PPh3
It is instructive to compare the deformation densities, which ligands by more than 80 kcal/mol, but the compound was
are associated with the formation of the electron-sharing σ and π reported to be stable up to 215 °C when it slowly decomposes
bonds in C2(CAACMe)2 with the dative σ and π bonds in after melting.230 The synthesis was reported in 1964, and the
B2(NHCMe)2 (Figure 12). Table 8 shows that the major compound was poorly characterized by giving only its high
components of ΔEorb in C2(CAACMe)2 come from two σ and melting point of 184 °C. It was sketched with the formula
two π orbital interactions. The associated deformation densities Ph3PNNPPh3, which is obviously wrong, giving rise to
Δρ1−4 and the singly occupied orbitals of the fragments along questioning the identity of the compound. A joint experimental
with the resulting MOs of the molecule are displayed in Figure and theoretical study by Holzmann et al. reinvestigated the
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Figure 16. Plot of the deformation densities Δρ of the pairwise orbital interactions for electron-sharing bonding between C2 in the excited 5Δg state
(see Figure 15) and two CAACMe ligands in C2(CAAC)2. (a) (CAACMe)−C2−(CAACMe) σ-interaction between the the 2σg+ MO of C2 and the
SOMO-3 of (CAACMe)2. (b) (CAACMe)−C2−(CAACMe) σ-interaction between the 1σu+ MO of C2 and the SOMO-2 of (CAACMe)2. (c)
(CAACMe)−C2−(CAACMe) π-interaction between the 1πg MO of C2 and the SOMO-1 of (CAACMe)2. (d) (CAACMe)−C2−(CAACMe) π-interaction
between the 1πu MO of C2 and the SOMO of (CAACMe)2. See ref 217.

Table 9. Calculated Free Energies (kcal/mol) at MP2/

TZVPP of the Metal−Ligand Bond Strengths in E2L2a
E2 + L → L-EE-L
E L = NHC L = PPh3
Group 14
C −158.2 −83.6
Si −84.2 −55.0
Ge −71.9 −49.4
Sn −66.8 −48.0
Pb −57.4 −44.4
Group 15
N 22.3 87.8
P −27.4 −16.2
As −21.3 6.4
Sb −25.9 Diss.
Bi −16.0 Diss.
a
The data are taken from ref 212.

structure and properties of the molecule.231 Following the

original simple synthetic protocol followed by an X-ray
measurement showed that the molecule is indeed N2(PPh3)2,
which has, however, a trans bent geometry of the core unit
(Figure 17a).
The inspection of the occupied orbitals (Figure 17b−e)
revealed a surprising electronic structure and bonding situation
of N2(PPh3)2. The out-of-plane π and π* orbitals of the N2
moiety are both occupied (HOMO−14 and HOMO), which Figure 17. (a) X-ray crystal structure of N2(PPh3)2. Selected bond
makes two in-plane MOs of the dinitrogen fragment available as lengths [Å] and angles [deg] with calculated values at RI-BP86/def2-
acceptor orbitals. The HOMO−1 and HOMO−15 are the in- TZVPP in brackets: N(1)−N(1) 1.497(2) [1.441], P(1)−N(1)
1.5819(12) [1.606], P(1)−N(1)−N(1a) 107.10(11) [112.6], P(1)−
phase (+,+) and out-of-phase (+,−) combination of the σ
N(1)−N(1a)−P(1a) 180.0 [180.0]. (b−e) Plot of relevant occupied
donation Ph3P→N2←PPh3. The electronic reference state of N2 orbitals of N2(PPh3)2.231 Reprinted with permission from ref 231.
is the highly excited (1)1Γg state which has the valence Copyright 2013 John Wiley and Sons.
configuration (1σg)2(1σu)2(1πu)2(2σg)2(1πg)2, where the 1πu′
and 1πg′ are vacant (Figure 18b). There is a formal excitation of
two electrons 1πu′ → 1πg from the X1Σg+ ground state (Figure combination of the σ lone-pair MOs of the PPh3 ligands. The
18a) to the (1)1Γg excited state. The bonding 1πu′ MO is the 1πu′ MO of N2 is much lower in energy than the antibonding
acceptor orbital for donation from the out-of-phase (+,−) 1πg′ orbital, which makes the associated HOMO−15 orbital of
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Chemical Reviews
Figure 18. Schematic view of the most important valence orbitals of N2
and the orbital occupation in (a) the X1Σg+ ground state and (b) 1Γg
excited state. Schematic view of (c) out-of-phase (+,−) donation of the
ligand σ orbitals into the vacant 1πu′ orbital of N2 and (d) in-phase (+,
+) donation of the ligand σ orbitals into the vacant 1πg′ orbital of N2.231
Reprinted with permission from ref 231. Copyright 2013 John Wiley
and Sons.
the complex more strongly stabilizing than the HOMO−1.
Figure 18c shows the Lewis structure of N2(PPh3)2, which
depicts the bonding situation in the molecule.
Table 10 shows the numerical results of the EDA-NOCV
calculation of N2(PPh3)2 with N2 in the (1)1Γg reference state as
Table 10. EDA-NOCV Results of N2(PPh3)2 Using the
Fragments N2 in the (1)1Γg Reference State and 2 PPh3a
Energy terms N2 + 2 PPh3
ΔEint −300.1
ΔEPauli 853.4
ΔEelstatb −377.4 (32.7%)
ΔEorbb −776.1 (67.3%)
ΔEσ1c,d −357.9 (46.1%)
ΔEσ2c,d −289.8 (37.3%)
ΔEπ1c,d −46.9 (6.0%)
ΔErestc −81.5 (10.6%)
a
Energy values in kcal/mol. The data are taken from ref 231. bThe
percentage values in parentheses give the contribution to the total
attractive interactions ΔEelstat + ΔEorb. cThe percentage values in
parentheses give the contribution to the total orbital interactions
ΔEorb. dThe notation σ1, σ2, π1 refers to the orbital pairs which are
associated with the deformation densities Δρ1, Δρ2, Δρ3 that are
shown in Figure 19.
acceptor fragment. The orbital term ΔEorb comprises two-thirds
of the total attraction between the donor and acceptor moieties.
There are three major components of ΔEorb, which can easily be
identified with the help of the associated deformation densities
Δρ (Figure 19) as in-phase (+,+) and out-of-phase (+,−) σ
donation Ph3P→N2←PPh3 into the unoccupied 1π′ orbitals of
N2 and the weaker Ph3P←N2→PPh3 π backdonation.
Table 10 shows that the intrinsic bond strength between N2 in
the (1)1Γg reference state and the PPh3 ligands is very large
(−300.1 kcal/mol). Thus, dinitrogen in the (1)1Γg state is a very
strong Lewis acid. This is due to the rather high electronegativity
of nitrogen and because the nitrogen atoms in have only
an electron sextet. However, the large interaction energy does
8808
Review
Figure 19. Plot of the deformation densities Δρ which are associated
with most important orbital interactions in N 2 (PPh 3 ) 2 . (a)
Deformation density Δρ1 due to donation Ph3P→N2←PPh3 into the
vacant in-plane π orbital of N2(1Γg). (b) Deformation density Δρ2 due
to donation Ph3P→N2←PPh3 into the vacant in-plane π* orbital of
N2(1Γg). (c) Deformation density Δρ3 due to π backdonation Ph3P←
N2→PPh3 from the occupied out-of-plane π orbital of N2(1Γg).231
Reprinted with permission from ref 231. Copyright 2013 John Wiley
and Sons.
not compensate for the geometrical and electronic relaxation of
the fragments, which amounts to ΔEprep = 349.3 kcal/mol. The
authors suggested that N2(PPh3)2 is a kinetically unusually
stable molecule where the dissociation reaction for loss of the
PPh3 ligands may be a symmetry forbidden reaction.231 The
activation barrier could not be calculated, because it requires
sophisticated approaches for a large molecule that were not
available to them. They estimated from an approximated
transition state that the barrier was higher than 25.1 kcal/mol
but lower than 67.6 kcal/mol, which is the calculated bond
dissociation energy for breaking the N−N bond.
7.3.5. O2, F2 and Related Molecules. The peculiarity of
O2, which possesses a triplet (3Σg−) ground state, was already
mentioned. It arises comprehensibly from the MO diagram in
Figure 8, which indicates that dioxygen has a double bond. The
EDA results for O2 in Table 4 must be taken with some caution.
It is not possible to assemble O2 in the (3Σg−) triplet state from
two oxygen atoms in the 3P state without a concomitant spin
change of one π electron (see Figure 9). This is how the EDA
calculation of O2 (3Σg−) was done.28 Table 4 shows that the total
π bonding contribution to the orbital interactions is 28.5%, a
little less than in N2, where π bonding makes up for 34.4% of
ΔEorb. According to the EDA results shown in Table 4, the
largest degree of π bonding contributions of the diatomic species
are found in B2 (40.8%) and C2 (48.2%). This is, because the σ
orbital interactions in B2 and C2 come from dative bonding while
the σ bonds in N2 and O2 are due to stronger electron-sharing
bonds.
The chemical bond in F2 comprises a single electron-sharing σ
bond, which is relatively weak. Difluorine is one of the rare
exceptions where the bond of a first octal-row atom is weaker
than in the heavier homologues. The BDE of Cl2 is calculated at
the same level of theory with De = 62.0 kcal/mol.28 The weak
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bond in difluorine is usually explained with the repulsion
between the lone-pair electrons at short distances. But the
strongest repulsion comes from the Pauli exchange interactions
between the electrons in the σ orbitals preventing shorter bonds.
Table 4 shows also that the Coulombic attraction in F2 is much
weaker than in O2 and particularly in N2. The rather long F−F
distance compared to O2 and N2 prevents an effective overlap of
the p(σ) electrons with the nucleus of the other fluorine. The
small stabilization energy of −6.2 kcal/mol of the π orbitals in F2
comes from the change in the mixing of the p(π) fluorine AOs of
the TZ2P basis set; it is an intraorbital polarization.
The highest lying occupied orbitals of F2 and O2 are
antibonding. Removal of two electrons in the dications should
enhance the covalent bonding, which might overcome the
Coulomb repulsion between the positively charged ions. In fact,
the covalent attraction in (X1Σg+) O22+ not only overcomes the
intrinsic Coulomb repulsion, it even enforces a shorter O−O
bond length in the dication (1.051 Å) than in neutral
isoelectronic N2 (1.102 Å). This paradoxical finding has been
noted before.232 The dioxygen dication O22+ has been
experimentally observed and was the subject of several
theoretical studies.232−236 It is a metastable species, which is
thermodynamically unstable toward dissociation in two O+
cations by 84.6 kcal/mol,232 but it lies in a deep potential well
of about 4.7 eV.233 Why does that O22+ have a shorter bond than
N2? Table 11 shows the EDA results for O22+, which may be
Table 11. EDA Results of Singlet O22+ and Triplet F22+
Species at the BP86/TZ2P-ZORA//BP86/def2-TZVPP
Levela
O22+d O22+e F22+
ΔEint 56.7 59.2 129.4
ΔEPauli 708.9 579.2 210.2
ΔEelstatb 126.5 144.0 233.0
ΔEorbb −778.8 (100%) −664.0 (100%) −313.9 (100%)
ΔE(σ)c −484.7 (62.2%) −418.4 (63.0%) −216.5 (69.0%)
ΔE(π)c −294.0 (37.8%) −245.6 (37.0%) −97.4 (31.0%)
r(E-E) 1.051 1.102 1.266
De 56.7 59.2 129.4
a
Energies are in kcal/mol and bond lengths r(E-E) in Å. bThe
percentage values in parentheses give the contribution to the total
attractive interactions ΔEelstat + ΔEorb. cThe percentage values in
parentheses give the contribution to the total orbital interactions
ΔEorb. dCalculated at the equilibrium distance. eCalculated using the
frozen equilibrium distance of isoelectronic N2.
compared with the data for N2 (Table 4). The energy values
indicate that the Pauli repulsion in the dication (ΔEPauli = 708.9
kcal/mol) is weaker than in N2 (ΔEPauli = 802.4 kcal/mol)
whereas the stabilizing orbital interactions in O22+ (ΔEorb =
−778.8 kcal/mol) are stronger than in N2 (ΔEorb = −729.8 kcal/
mol). The orbital contraction in the dication due to the positive
charge has obviously a much stronger effect on the Pauli
repulsion than on the orbital interactions. Although the
interatomic distance in O22+ is smaller than in N2, the Pauli
repulsion becomes weaker, because the overlap of the occupied
orbitals in the dication becomes smaller due to the charge
induced contraction. The overlap between occupied and vacant
orbitals in O22+ is reduced to a lesser extent, and therefore, the
orbital interactions in the dication become stronger than in N2.
The effect of the different energy terms on the bond length of
O22+ becomes obvious by comparing the calculated values at
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equilibrium distance and the frozen distance of N2. Table 11
shows that the Pauli repulsion in O22+ at the shorter equilibrium
bond length (1.051 Å) is stronger than at the frozen N−N
distance (1.102 Å), but this is overcompensated by the stronger
covalent interactions. The Coulomb repulsion at the shorter
equilibrium distance is weaker than at the longer distance,
because the increase of the electron−nucleus attraction is larger
than the electron−electron and nucleus−nucleus repulsion. All
this is somewhat counterintuitive for a classical viewpoint, but it
becomes understandable using quantum theoretical argu-
ments.28
Table 11 shows that the Coulomb contribution in O22+ is
repulsive, which makes the overall interaction energy ΔEint and
the bond dissociation energy De positive. It means that the bond
dissociation energy is not always an adequate indicator for the
strength of a chemical bond. This holds for all energy-rich
molecules, where bond-breaking reactions are exergonic. It can
be argued that the activation energy for breaking the bond, ΔE⧧,
may be used instead, which would involve the calculation of the
activation barrier. However, bond breaking involves a change in
the electronic structure when one goes from the molecule to the
fragments, which may not be related to the intrinsic binding
interactions at equilibrium. A case example is the CC double
bond in C2F4, which is discussed below in section 8.237 A direct
probe for the intrinsic strength of a chemical bond is the local
mode force constant, which was introduced by Cremer and co-
workers as a universal measure of the bond strength.200,238−241
The force constant is the second derivative of the energy with
respect to the equilibrium coordinates, which does not require
the energy of the fragments or the transition state as a reference
for bond strength. It may thus be used for stable and metastable
species alike.
Table 11 also shows the EDA results for the difluorine
dication F22+ in the triplet (X3Σg−) ground state.242,243 The F−F
bond in the dication (1.266 Å) is much shorter than in neutral F2
(1.420 Å), but it is not shorter than in isoelectronic O2 (1.224
Å). The data for the energy values show that the Pauli repulsion
in F22+ is much weaker (ΔEPauli = 210.2 kcal/mol) than in
neutral O2 (ΔEPauli = 464.9 kcal/mol, Table 4) but the orbital
interactions in F22+ (ΔEorb = −313.9 kcal/mol) are also weaker
than in O2 (ΔEorb = −447.1 kcal/mol). It appears that the
interactions in the isoelectronic pair F22+/O2 are somewhat
different from the system O22+/N2, which may be due to the
occurrence of Pauli repulsion between π electrons in the latter
pair. But the conclusion remains that the removal of electrons
from antibonding orbitals is able to strongly enhance the
covalent interactions, which may lead to significantly shorter
bonds overcoming strong Coulomb repulsion.
The following conclusions arise from this section:
• The trend of the bond strength of the first octal-row
diatomic molecules can conclusively be explained with the
results of the EDA-NOCV calculations, which provide
further insight into the nature of the interactions in terms
of Coulombic attraction/repulsion, Pauli repulsion, and
orbital (covalent) bonding. Accordingly, the very weak
attraction in Be2 is due to Pauli repulsion but not to
mutual energy compensation of the occupied bonding
and antibonding valence orbitals. Likewise, the rather
weak bond in F2 is caused by the Pauli repulsion of the
electrons in the σ orbitals rather than repulsion of the π
lone-pair electrons.
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• The covalent bonding in the dications (X1Σg+) O22+ and
(X3Σg−) F22+ is stronger and the bonds are shorter than in
the neutral parent molecules because the Pauli repulsion
is weaker in the charged species due to the orbital
contraction. The covalent bonding in O22+ is even
stronger than in N2. The Coulomb repulsion makes the
dications thermodynamically unstable. The force con-
stant is more suitable as measure for the intrinsic strength
of a bond than the bond dissociation energy.
• The consideration of the occupied and vacant orbitals in
the ground and excited states of E2 provides an
understanding of complexes where the diatomic species
are stabilized by donor ligands L→E2←L. This led to the
synthesis of the first compound with a boron−boron
triple bond NHCR→B2←NHCR that is stable under
ambient temperatures.
• The donor strength in complexes L→E2←L may
overcompensate the electronic excitation energy of E2
from the ground to the excited reference state in the
adduct, which leads to thermodynamically stable
compounds. However, there are molecules like L→
N2←L (L = NHC, PPh3) where N2 is in the high lying
(1)1Γg state, which are calculated to be unstable toward
dissociation of N2, and yet, they can easily be isolated.
This is likely because the extrusion reaction is a symmetry
forbidden process.
7.4. Chemical Bonding in Heavier Main-Group Compounds
There is ubiquituous chemical evidence that the structures and
reactivities of the first octal-row atoms exhibit siginificant
differences from the heavier homologues. This is particularly
evident when one compares the organic chemistry of carbon
with silicon chemistry. The statement “Silicon is weird” clearly
characterizes this finding from an organic chemist point of
view.244 The difficulties to understand the large differences
between molecules of the first octal row and higher homologues
stem from the fact that the heuristic bonding models, which were
developed during the last century, received their input mainly
from observations which were made with compounds of the first
octal-row atoms, henceforth also called lighter elements, for
which experimental data were available. The neural network of
chemical information, which was used to develop such models,
was mainly fed with results that came from first octal-row
molecules. Compounds of the heavier elements, which exhibit
different properties, were initially considered as exceptions, for
which sometimes peculiar explanations were made. This led to
difficulties when the information about molecules of the heavier
elements increased. The unequal structures and reactivities of
heavier main-group compounds could no longer be considered
as anomalies. But the bonding models that were suggested to
rationalize their behavior were still mainly based on extensions
of the existing schemes with some ad-hoc additions. Some of
them were simple prescriptions for writing formulas that appear
to address the peculiar bonding situations of the heavier
molecules without which a sound theoretical basis for the
differences between lighter and heavier main-group compounds
was given.
The nature of the chemical bond in heavier main-group
compounds has been discussed from a quantum chemical point
of view in a review article by Kutzelnigg in 1984.245 The author
presents the fundamental differences between the valence shells
of the lighter and the heavier main group atoms, and he discusses
their effects on the structures and bonding situations of the
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molecules. There is one particular feature of the atoms, which
can be considered as essential for the different chemistry of the
two groups. It concerns the ratio of the radii of the (n)s and (n)p
valence AOs of the atoms, which significantly changes from the
first to the higher octal-row atoms. The 2p orbitals of the first
octal-row atoms may penetrate rather deeply into the core,
because there are no lower lying occupied p functions, whereas
the 2s orbitals are constrained to be orthogonal to the 1s AO.
The radii of 2s and 2p orbitals are thus very similar, which leads
to effective sp hybridization in chemical bonds of the lighter
atoms. In contrast, the occupied (n)p AOs (n > 2) of the heavier
atoms are antisymmetric to the p core orbitals, which causes
larger radii for the (n)p than for the respective ns AOs. The
spatial regions of (n)s and (n)p AOs (n > 2) are more separate
than those of 2s and 2p AOs, which leads to less effective
hybridization of the heavier main-group atoms.246 Looking from
an aufbau principle of atomic structure, chemical bonding of the
heavier main-group atoms exhibits “normal” behavior, whereas the
f irst octal-row atoms are “anormal”, because the valence p AOs are
not affected by lower lying p orbitals. The difference between the
relative size of the light and heavier main group atoms is
schematically shown in Figure 20.
Figure 20. Schematic representation of the relative size of the (n)s and
(n)p AOs in atoms (a) of the first octal row and (b) in heavier main-
group atoms.
The relative size of the (n)s and (n)p AOs of the main-group
elements is a significant factor for the nature of the chemical
bonds and the reactivities of main-group compounds. An
approaching atom B “sees” the (n)p AOs earlier than the (n)s
AOs (n > 2) of A. In less colloquial wording, it means that the
interference of the wave function between B and the valence p
AO of heavy atom A occurs earlier and is larger than with the
valence s AO. Kutzelnigg analyzed the Mulliken gross
population at the central atoms in EH4 (E = C, Si) and found
that the hybridization at carbon is sp3 while it is ∼sp2 in SiH4,
although both molecules have Td symmetry.245 Table 12 shows
the hybridization of the E-X localized orbitals in tetrahedral (Td)
EX4 (E = C−Pb; X = H, Cl) given by the NLMO (Natural
Localized MO) method.68−71 Only CH4 shows a perfect sp3
hybridization, while the E−H bonds in the heavier EH4
homologues possess ∼sp2 hybridized orbitals at atom E. The
chlorine systems ECl4 deviate even more strongly from sp3
hybridization. The percentage p-character of the E-Cl bonds at
atom E is much higher than one would expect from the sp3
model. The Pb−Cl bonds have even nearly equal s and p orbital
contribution at Pb. Note that the correct hybridization is only
given by the NLMOs, which include the nondiagonal elements
of the Fock matrix. The standard NBOs give perfect sp3
hybridization for all EX4 species.
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Table 12. NLMO Analysis of EX4 (E = C−Pb; X = H, Cl) at than for the respective (n)s AOs of the heavier main-
the HF/def2-TZVPP Level Using NBO 6.0a group atoms.
q Pol. Hybrid.
• Effective spx hybridization is only possible for the first
Molecule E X P(E−X) E% X% ns:np:(n−1)d
octal-row atoms, because the 2s and 2p AOs have similar
CH4 −0.74 0.19 0.97 59 41 25:75:0 radii. Chemical bonds of the heavier atoms have a rising
SiH4 0.85 −0.21 0.93 39 61 33:66:1 degree of higher %p character, and the (n)s orbitals
GeH4 0.74 −0.18 0.94 41 59 33:67:0 become gradually less prone to be engaged in chemical
SnH4 0.96 −0.24 0.91 38 62 35:65:0 bonding. This stabilizes low-valent compounds of the
PbH4 0.74 −0.18 0.92 41 59 36:64:0 heavier main-group atoms.
CCl4 −0.17 0.04 1.02 49 51 30:70:0
SiCl4 1.51 −0.38 0.88 26 74 37:60:3 7.4.1. Hypervalent Molecules: Valence, Orbital Sym-
GeCl4 1.64 −0.41 0.91 25 75 43:56:1 metry, and 3-Center, 4-Electron Bonding. In order to
SnCl4 1.87 −0.47 0.77 23 77 42:57:1 address the topic of hypervalence, one must first clarify what is
PbCl4 1.74 −0.44 0.76 25 75 49:51:0 meant by the term “valence”. According to the IUPAC, valence
a
Atomic partial charges q, Wiberg bond order P(E−X), polarization, is defined as “The maximum number of univalent atoms (originally
and hybridization of atom E in the E−X bond. hydrogen or chlorine atoms) that may combine with an atom of the
element under consideration, or with a f ragment, or for which an
atom of this element can be substituted.”251 Accordingly, molecules
The differences in the structures of molecules between first such as PF5 and SF6 are hypervalent, because they doubtlessly
and higher octal-row elements can thus be traced back to the possess five and six bonds at phosphorus/sulfur. However,
radii of the valence s and p AOs. This shall be demonstrated with quantum chemistry suggests that chemical bonding and thus
selected examples below. We also want to mention relevant valence are associated with the molecular orbitals, which are
theoretical studies by Kaupp, who analyzed the bonding used to describe the chemical bonds. Then the question arises,
situation in heavier main-group compounds paricularly of the which atomic orbitals are effectively engaged in the interference
sixth row of the periodic system.247−250 of the orbitals building the wave function. Since the s and p AOs
There are two prominent observations that distinguish can be occupied by a maximum of eight electrons, it seems
heavier main-group compounds from compounds of the lighter difficult to assign more than four bonds to an atom, which uses
homologues which shall be analyzed and discussed in this only its valence (n)s and (n)p AOs for covalent bonding. A
section. One phenomenon concerns the number of electron-pair simple explanation for the observation of stable molecules with
bonds and the coordination number of the atoms. Heavier main- more than four bonds such as PF5 and SF6 considers the (n)d
group atoms can have more than four bonds in stable molecules. orbitals, which are available for heavier main-group atoms where
This is essentially unknown for first octal-row atoms. Classical n ≥ 3. Early work suggested that hypervalent molecules possess
examples are SF6 and PF5, which are discussed below. The (n)sx(n)py(n)dz hybridized bonds. Accordingly, hypervalent
question if such molecules should be considered as hypervalent molecules would not obey the octet rule, which states that a
and if they obey the octet rule will also be considered. maximum of eight electrons are used for covalent bonding.
The second topic concerns the observation that compounds An alternative suggestion, which uses only (n)s and (n)p AOs
with multiple bonds between heavier main-group atoms are for covalent bonding in hypervalent molecules, was suggested
much more difficult to isolate and that they often possess very independently by Rundle252−254 and Pimentel.255 It is now
different equilibrium geometries than the first octal-row known as the 3-center, 4-electron bonding model, and it was
analogues. Classical examples are ethylene and acetylene and adapted by Coulson to VB theory.256 It is worthwhile to read the
their heavier group-14 homologues. The standard textbook original paper, because it already uses the symmetry of the
explanation suggests that the overlap of the p(π) AOs of the molecular orbitals for explaining chemical bonding in molecules
heavier atoms is much smaller than for lighter atoms, because of that possess an excess number of electron pairs than required by
the longer bonds of the former. It has been known for a long time the octet rule. The authors discuss the bonding in various
that this suggestion is not valid, because the p(π) AOs of the molecules such as I5−, XeF4, XeF2, HF2−, and X3−.252−255 It is
heavier atoms are more diffuse than for lighter atoms, which shown that the covalent bonds in the molecules may be
largely compensates for the longer bond. Furthermore, the described without invoking the use of higher energy basis
alleged weakening of the π bonds as reason for the experimental functions, as it was previously advocated by Pauling11 and by
findings is questionable, because the overlap of the σ AOs of the Kimball.257 The 3-center, 4-electron model can also be applied
heavier atoms is also affected by the longer distance. We shall to the π bonds in the allyl anion C3H5−. The basic feature is
present an explanation for the observations, which is based on displayed in Figure 21, which uses a model system of three atoms
the valence shell structure of the atoms. A3 possessing one AO each.
The following conclusions arise from this section: The three atomic basis functions lead to three MOs φ1−3,
• The most important difference between atoms of the first which are shown in ascending energy order. Covalent bonding
and higher octal rows of the periodic system, which comes from the occupation of φ1, which is totally symmetric.
determines the experimentally observed variance of their There is no covalent bonding between the central and the
structures and reactivities, is the relative size of the valence terminal atoms in φ2, which has one node. But there is still a
s and p orbitals and not the availability of d orbitals for the stabilizing contribution from electrons that occupy φ2, because
heavier elements. The (n)p AOs for n > 2 are, as of the Coulomb attraction between the nucleus of the central
determined by the Pauli principle, antisymmetric to the p atom and the electrons occupying the MO. The energy lowering
core orbitals, unlike the 2p AOs, which experience no due to occupation of φ2 is less than that of the electrons in φ1,
lower lying p orbitals. This causes larger radii for the (n)p but the total system is further stabilized. The occupation of φ2 in
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Figure 21. Schematic representation of the molecular orbitals φ1 − φ3
of a 3-center, 4-electron bond.
A3 plays a similar role as the occupation of the 1eg MO in SF6,
which is discussed below (Figure 22).
The important result of these early works252−255 is the finding
that molecules with covalent bonds, which possess an excess
number of electron pairs as required by the octet rule, can be
described using only their (n)s and (n)p orbitals for the
interference of the wave function. When accurate quantum
chemical calculations became available later, it was shown that
the (n)d AOs of heavy main-group atoms are not genuine
valence orbitals in hypervalent molecules but rather serve as
polarization functions. The reason why hypervalent molecules
Figure 22. Splitting of the (n)s and (n)p AOs of a main-group atom E (a) in the octahedral field of six ligands X in EX6 and (b) in the trigonal pyramidal
field of five ligands X in EX5.
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are stable only for the heavier atoms lies in the atomic size. First
octal row atoms A are too small and cannot accommodate more
than four atoms in AXn because the X−X Pauli repulsion
prevents the formation of stable species with n > 4. The 3-center
4-electron bonding model is an early version of the MO derived
models, which uses the symmetry of the orbitals for the
explanation of structures and reactivity that became so
prominent in the 1970s.
7.4.2. Hypervalent Molecules: SF6 and PF5. The
molecules SF6 and PF5 may be considered as archetypical
examples for the validity problem of the octet rule and the
chemical bonds in hypervalent compounds. There are definitely
six and five bonds in the respective molecules, which pose the
question about the correct representation of the bonding
situation with Lewis structures in accordance with the octet rule.
There have been numerous discussions and suggestions about
the usefulness of Lewis structures and the octet rule for
hypervalent molecules, which are perhaps better termed as
hypercoordinated species. The problem can straightforwardly
be addressed with the help of the symmetry of the molecular
orbitals describing the valence electrons in the molecule.
Figure 22a schematically shows the σ MOs of model
compound EX6 where the central atom E has (n)s and (n)p
valence functions. In the octahedral (Oh) ligand field in EX6, the
(n)s and (n)p atomic orbitals of atom E split into an a1g and a
triply degenerate set of t1u AOs, whereas the six σ orbitals of the
ligand cage X6 are divided into a1g, t1u, and eg MOs. The
molecule SF6 has 12 valence electrons that occupy six σ MOs.
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Figure 22a shows that only four MOs in EX6 (a1g and t1u) have
the right symmetry to enable interference between the AOs of
atom E and the ligands cages. The degenerate eg MO does not
induce covalent E−X bonding. This does not mean that the
electrons in the eg MO do not contribute to the stabilization of
the molecule. The electronic charge of the ligand cage X6 may be
strongly stabilized through Coulomb interactions with the
nucleus of atom E.258 This also shows the limitation of the
model of orbital interactions (covalent bonding) for describing
chemical bonding. There are other forces such as Pauli repulsion
and Coulombic interactions, which strongly influence the
chemical bond. It is a widely held belief that electrostatic
interactions between neutral atoms are weak or may even be
repulsive, which for most molecules is not correct.28,177,259 Thus,
there are actually only four electron-pair bonds in octahedral
EX6 that come from the interference of the wave functions of the
atoms, which fully agrees with the octet rule. This information is
only available by inspection of the symmetry of the MO wave
function. But the orbitals are delocalized over more than two
atoms (seven atoms in the 1a1g MO and three atoms in each 1t1u
components) and the problem is to convert the delocalized
picture of the MO calculation into the model of localized Lewis
structures. Much of the difficulties and controversies about
chemical bonding in molecules in the literature can be traced
back to the discrepancy between the viewpoints of delocalized
and localized bonds. The adherence to two-center bonds in the
works of Gilbert Lewis and Linus Pauling can be identified as a
severe limitation of the viewpoint on chemical bonding, and it is
the source of much confusion still today. This is surprising,
because the ground-breaking study by Erich Hückel on
aromaticity showed in the 1930s already the advantages if the
description of chemical bonding is not restricted to a localized
model.20
The connection of the octet rule to the bonding situation in
PF5 is similar to SF6 but with an additional facet. Figure 22b
shows that the AOs of E and σ MOs of X5 split in the D3h
symmetric model compound EX5 and give rise to σ orbitals
possessing a1′, a2″, and e′ symmetry, which are occupied by ten
electrons. The 1a1′, 1a2″, and the degenerate 1e′ MOs are
bonding orbitals that give four delocalized electron-pair bonds,
which result from the interference of the wave functions. The
2a1′ orbital is the HOMO in EX5, but the coefficient of the (n)s
valence AO is very small, which makes it effectively a
nonbonding MO. There is negligible interference between the
atomic orbitals of phosphorus and fluorine in the 2a1′ MO.
Covalent bonding refers to the number of bonds, which are due
to the interference of the wave functions. There are four such
doubly occupied MOs in the molecules. The bonding situation
in PF5 is thus in agreement with the octet rule.63,260
How may the information gained by the MO model be
expressed by Lewis structures? The most common sketches of
Lewis formulas for SF6 and PF5 obeying the octet rule depict one
of 14 “resonance forms” for SF6 and one of five for PF5 as shown
in Figure 23, which require formally charged fragments. It
becomes obvious that the presentation of the chemical bonds is
clumsy and the use of charged species may give rise to a
misleading interpretation of the nature of the bonding. The
“ionic−covalent” resonance forms in Figure 23 must not be
interpreted as indication for the appearance of ionic interactions.
The charges that show up in the Lewis structures are only formal,
and they have no physical relevance. The sometimes accidental
agreement between formal charges and actual charge distribu-
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Figure 23. Lewis structures for (a) SF6 and (b) PF5 that obey the octet
rule.
tion in a molecule should not be used as evidence for the
correctness of the model.
The following conclusions arise from this section:
• The question of hypervalence can only be addressed when
valence is defined.
• Covalent bonding of main-group compounds usually
involves the atomic valence s and p orbitals. Molecular
orbitals can be constructed so that they are filled with
more than eight electrons, but the individual atoms do not
receive more than eight electrons in their valence shell.
• The Lewis model of localized electron pairs is not well
suited for describing hypervalent molecules.
• The 3-center, 4-electron MO model of Rundle and
Pimentel provides a simple rationale for the bonding in
hypervalent molecules. It shows that the octet rule is
fulfilled in molecules where a main-group atom has more
than four bonds. The stabilization of the excessive
electrons comes from the electrostatic stabilization,
which is an important factor in all covalent bonds.
• The bonding in SF6 and PF5 is an archetypical example for
formally hypervalent molecules that still obey the octet
rule. There are only four doubly occupied valence MOs in
SF6, which have contributions from the s and p AOs of
sulfur. The symmetry of the MOs is the key for
understanding the interplay between the octet rule and
the number of bonds. The excess electrons in PF5 occupy
an antibonding MO, which has a negligible contribution
from the s and p AOs of phosphorus.
7.4.3. Multiple Bonds of Heavy Diatomic Molecules
Na2−Cl2 and N2−Bi2 and Related Molecules. A commonly
made statement which is found in many textbooks of chemistry
claims that the π bonds between heavy main-group atoms are
weaker than between first octal-row elements. Table 13 gives the
EDA results for the diatomic molecues Na2−Cl2 (second-row
sweep), which may be compared with the data for the first-row
species Li2−F2 (Table 4).28 The BDEs of the heavier molecules
are smaller than those of the lighter systems, except for the
dihalogens F2 and Cl2, which agrees with the experimental
findings. The reason for the exceptionally weak F−F bond has
been discussed in section 7.3.5. Note that Si2 has a X3Σg− ground
state whereas the valence isoelectronic C2 has a X1Σg+ ground
state. A comparison of the nature of the bonding between the
different atoms should be done for the same spin state.
The trend of weaker bonds for heavier atoms, which is a
general feature for the elements of the periodic system, comes
from the more weakly bonded valence electrons. The first
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Table 13. Energy Partitioning Analysis of the Second Row Dimers E2 (E = Na−Cl) in C2v at BP86/TZ2Pa
E Na Mg Al Si Si P S Cl
State Σg+
1 1
Σg+ 3
Σg− 3
Σg− 1
Σg+ 1
Σg+ 3
Σg− 1
Σg+
ΔEint −16.3 −1.7 −35.6 −78.3 −56.5 −118.5 −112.2 −64.6
ΔEPauli 5.1 9.4 42.9 184.2 79.5 317.4 247.3 129.1
ΔEelstatb −10.7 (50.1%) −5.2 (46.2%) −15.6 (19.9%) −123.7 (47.1%) −4.4 (3.2%) −186.3 (42.7%) −121.8 (33.9%) −51.1 (26.4%)
ΔEorbb −10.7 (49.9%) −6.0 (53.8%) −62.9 (80.1%) −138.9 (52.9%) −131.6 (96.8%) −249.7 (57.3%) −237.7 (66.1%) −142.7 (73.6%)
ΔΕ(σ)c −10.7 (100.0%) −6.0 (100.0%) −26.1 (41.5%) −91.7 (66.0%) −50.1 (38.1%) −148.6 (59.5%) −154.0 (64.8%) −126.7 (88.8%)
ΔΕ(π)c 0.0 (<0.1%) 0.0 (<0.1%) −36.8 (58.4%) −47.2 (34.0%) −81.4 (62.0%) −101.0 (40.4%) −83.7 (35.2%) −15.9 (10.2%)
ΔEcorre 0.3 0.0 1.1 1.7 1.6 1.3 3.0 2.6
De d 16.0 (17.1) 1.7 (1.2) 34.5 (35.1) 76.6 (74.8) 54.8 117.2 (117.2) 109.2 (101.8) 62.0 (58.0)
E−Ed 3.095 (3.079) 3.607 (3.890) 2.510 (2.466) 2.303 (2.246) 2.071 1.911 (1.893) 1.921 (1.889) 2.023 (1.987)
a
All energies in kcal/mol, distances E−E in Å, all dissociation energies were calculated for the dissociation in the ground state atoms (Na: 2S; Mg:
1
S; Al: 2P; Si: 3P; P: 4S; S: 3P ; Cl: 2P). Data are taken from ref 28. bValues in parentheses give the percentage contribution to the total attractive
interactions ΔEelstat + ΔEorb. cValues in parentheses give the percentage contribution to the total orbital interactions ΔEorb. dExperimental values in
parentheses from ref 24. eCorrection for the spin polarization.

Table 14. Energy Partitioning Analysis of the E−E Bond for E = N−Bi (BP86/TZ2P)a
N2 P2 As2 Sb2 Bi2
ΔEint −240.2 −118.5 −97.3 −74.2 −64.6
ΔEPauli 802.2 317.6 276.8 219.3 201.9
ΔEElstatb −312.8 (30.0%) −186.3 (42.7%) −181.5 (48.5%) −159.0 (54.2%) −150.8 (56.6%)
ΔEOrbb −729.6 (70.0%) −249.8 (57.3%) −192.7 (51.5%) −134.5 (45.8%) −115.7 (43.4%)
ΔEσc −478.7 (65.6%) −148.7 (59.5%) −116.2 (60.3%) −81.0 (60.3%) −72.4 (62.6%)
ΔEπc −250.9 (34.4%) −101.1 (40.5%) −76.4 (39.7%) −53.4 (39.7%) −43.2 (37.4%)
Overlap σe 1.59 (68.2%) 1.49 (70.3%) 1.40 (70.7%) 1.36 (72.3%) 1.21 (70.8%)
Overlap πe 0.74 (31.8%) 0.63 (29.7%) 0.58 (29.3%) 0.52 (27.7%) 0.50 (29.2%)
Hybridization of the σ bond s: 37.5% s: 20.8% s: 15.4% s: 11.6% s: 8.0%
p: 61.9% p: 77.8% p: 83.9% p: 87.9% p: 91.9%
R(E−E)d 1.102 (1.098) 1.911 (1.893) 2.113 (2.103) 2.504 (2.48) 2.660 (2.660)
De 240.2 118.5 97.3 74.2 64.6
D0d 236.9 (225.0) 117.4 (116.1) 96.7 (91.3) 73.8 (71.3) 64.3 (47.0)
a
The interacting fragments are two atoms E in the 4S ground state (s2px1py1pz1). Energy values are given in kcal/mol. Bond lengths are given in Å.
The values are taken from ref 261. bThe values in parentheses give the percentage contribution to the total attractive interactions ΔEelstat + ΔEorb.
c
The values in parentheses give the percentage contribution to the total orbital interactions ΔEorb. dExperimental results are given in parentheses.
e
The values in parentheses give the percentage contribution to the total orbital overlap.

ionization energies decrease from top to bottom of the periodic
system within each group. Exceptions arise when inner shells are
filled or when relativistic effects become important, which are
discussed further below. Table 13 shows that the percentage
contribution of the electrostatic attraction ΔEelstat to the bonds
in the second-row dimers is higher than in the first-row dimers.
This can be explained with the larger nuclei and the bigger
electronic charges of the former, which compensate for the
longer bonds. The most interesting result for the present topic
arises from comparison of the π contribution to the orbital
interactions ΔEorb between Al2−S2 and B2−O2. The data in
Table 13 suggest that the π bonding in the heavier diatomic
molecules contributes more to the covalent bonding than in the
lighter species.
The second-row sweep Na2−Cl2 shown in Table 13 shall be
complemented by a group-15 sweep of the diatomic species N2−
Bi2. The numerical results of the bonding analysis are shown in
Table 14.261 The bond strength of the molecules given by the
ΔEint (= −De) values exhibits the expected weakening from top
to bottom N2 ≫ P2 > As2 > Sb2 > Bi2. The relative Coulombic
attraction to the overall binding shows the opposite trend, which
is due to the increase of the positive charge of the nuclei. The
contribution of π bonding to the overall orbital interaction
increases from nitrogen to phosphorus and then becomes
8814
slightly less, but the percentage value of π bonding in Bi2 is still
higher (37.4%) than in N2 (34.4%). The overlap of the p(π)
orbitals decreases from nitrogen to the heavier atoms, but the
same trend is observed for the overlap of the σ orbitals. Note that
the hybridization of the σ bonds changes significantly toward
higher %p character from N2 to the heavier atoms. This comes
from the change in the radii ratio of the valence s and p AOs
(Figure 20).
Numerous complexes have been synthesized in the recent
past where heavier diatomic species E2 of the third and higher
octal row of the periodic system are stabilized by donor ligands
L→E2←L where L is mostly a NHC or CAAC carbene ligand.262
The bonding situation in these adducts has been explained in
terms of donor−acceptor interactions between E2 in an
electronically excited reference state and the carbene σ-donor
ligands in a similar fashion as for the first octal-row adducts,
which were discussed above.263,264 Since there are no new
aspects about the nature of the bonding in the heavier
complexes, we do not present them here. The interested reader
can find the details in the original publications and in recent
review articles.49,55,56
The increase of the π contribution to the covalent interactions
in the heavier diatomic molecules is in contrast to the textbook
knowledge that π bonding between heavier main-group atoms is
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particularly weak and, therefore, heavier main-group com- only stretched by 16.2% relative to P2 (1.911 Å). This is a hint
pounds with multiple bonds are much less stable than toward a possible explanation. More detailed information is
homologues of the lighter elements. Since chemical evidence available from EDA calculations of the diatomic and tetraatomic
for the latter finding is ubiquitous, other factors rather than molecules.
weaker π bonding must be responsible for the observation and Table 15 shows the EDA results for E4 (E = N, P). Note that
different explanations have to be provided. This is done in the the N−N and P−P bonds have a similarly small %s contribution;
following sections.
7.4.4. Multiple Bonds of Heavy Main-Group Atoms: Table 15. Energy Partitioning Analysis of E4 (E = N, P)
N2/N4 vs P2/P4. The most common allotropes of nitrogen and (BP86/TZ2P) and Comparison with E2a
phosphorus are gaseous N2 and tetrahedral P4 (white
E4 1/4 E4 1/2 E2
phosphorus), whose structures and relative energies may be
used as prototype to analyze the different chemical bonds of E=N
atoms of the first and second row of the periodic system. ΔEint −322.6 −80.7 −120.1
Tetrahedral N4 (Td) is an energetically high-lying minimum ΔEPauli 1636.6 409.2 401.1
species, which is experimentally unknown so far but has been the ΔEelstatb −705.4 (36.0%) −176.4 −156.4 (30.0%)
(36.0%)
subject of quantum chemical studies.265 Experimental data for
ΔEorbb −1253.7 −313.4 −364.8 (70.0%)
N2, P2, and P4 are available from the literature.24,266 (64.0%) (64.0%)
Figure 24 shows the calculated geometries of the diatomic and ΔEσc −1253.7 −313.4 −239.4 (65.6%)
tetraatomic molecules.267,268 The computed reaction energies (100.0%) (100.0%)
ΔEσ/nf −156.7 −104.5 −239.4
ΔEπc −125.5 (34.4%)
Hybridizatione of the s: 7.0% s: 7.0% s: 37.5%
σ bond p: 92.5% p: 92.5% p: 61.9%
R(N−N) 1.464 1.464 1.102 (1.098)g
E=P
ΔEint −293.1 −73.3 −59.3
ΔEPauli 972.3 243.1 158.8
ΔEelstatb −545.7 (43.1%) −136.4 −93.2 (42.7%)
(43.1%)
ΔEorbb −719.8 (56.9%) −180.0 −124.9 (57.3%)
(56.9%)
ΔEσc −719.8 −180.0 −74.4 (59.5%)
(100.0%) (100.0%)
ΔEσ/nf −120.0 −60.0 −74.4
ΔEπc −50.6 (40.5%)
Hybridizatione of the s: 5.2% s: 5.2% s: 20.8%
σ bond p: 93.2% p: 93.2% p: 77.8%
R(P−P) 2.221 (2.223)d 2.221 1.911 (1.893)g
a
The interacting fragments are four atoms E in the 4S ground state
(s2px1py1pz1). Bond lengths are given in Å. Energy values are given in
kcal/mol. The data are taken from refs 261. bThe values in
parentheses give the percentage contribution to the total attractive
interactions ΔEelstat + ΔEorb. cThe values in parentheses give the
Figure 24. Calculated bond lengths [Å] of E2 and (Td) E4 (E = N, P) percentage contribution to the total orbital interactions ΔEorb.
d
and dimerization energies De of E2 at BP86/TZ2P. Experimental bond Experimental value, ref 266. eThere is a small contribution from
lengths are given in parentheses. Reprinted with permission from ref the d polarization functions. fn = Number of bonds. gExperimental
267. Copyright 2014 Springer Nature. value, ref 24.

for formation of the tetrahedral species are striking evidence for

the drastic variation of nitrogen and phosphorus bonding:
2N2 → N4(Td) +158.9 kcal/mol
2P2 → P4 (Td) −59.7 kcal/mol
The enormous energy difference of 218.6 kcal/mol between
reactions 23 and 24 suggests a fundamental difference between
the strengths of the nitrogen and phosphorus bonds in the
diatomic and tetratomic isomers. The above results show that
different π bond strength in the diatomic species cannot be the
reason for the diverse stability order. Inspection of Figure 24
shows that tetrahedral isomers of both elements have longer
bonds than the diatomic species, but the bond lengthening of
nitrogen is more pronounced than that of phosphorus. The
calculated N−N bond length in N4 (1.464 Å) is 32.8% longer
than in N2 (1.102 Å), whereas the P−P bond in P4 (2.221 Å) is
the change in the hybridization compared with the diatomic
molecules (Table 14) is particularly large for N2. Table 15 gives
(23) the values for E4 divided by four and the data for E2 divided by
two for the direct comparison of the isomers. The values in the
(24)
two final columns refer to the energy values per atom. It becomes
obvious that the nitrogen atoms in N2 are stabilized with respect
to N4 whereas the phosphorus atoms in P4 are lower in energy
than in P2. Inspection of the three energy components indicates
that the reverse in stability is also found for the orbital term
ΔEorb but not for ΔEelstat and ΔEPauli. The covalent interactions
stabilize the atoms in N2 much stronger than in N4, whereas the
orbital interactions stabilize phosphorus in P4 more than in P2.
The diatomic molecules E2 have one σ and two degenerate π
bonds, whereas E4 has six σ bonds. Thus, there are three bonds
per atom in E2 (one σ, two π) and in E4 (three σ). Table 15
shows that the σ bond strength per atom in E2 is higher than the
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Figure 25. Variation of the energy terms of the EDA at different bond lengths of (a) N2 and (b) P2 at BP86/TZ2P. Reprinted with permission from ref
267. Copyright 2014 Springer Nature.
π bond strength for both N and P. The crucial difference
between nitrogen and phosphorus is the change of the σ bond
strength from E2 to E4. The σ bond strength per atom in N4
(−104.5 kcal/mol) is drastically less than in N2 (−239.4 kcal/
mol) and becomes even lower than the strength of the π bond in
N2 (−125.5 kcal/mol). The σ bond strength in P4 (−60.0 kcal/
mol) is also lower than in diatomic P2 (−74.4 kcal/mol), but the
weakening is clearly less than for nitrogen and it remains
stronger than the π bond strength in P2 (−50.6 kcal/mol). The
dramatic weakening of the chemical bonds in N4, which leads to the
overall much lower stability of the nitrogen tetramer and the reverse
energy shif t of the phosphorus homologues, is related to the σ bonds
and not to π bonding.
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Review
But what is the driving force for the drastically weaker N−N σ
bonds in the tetramer than in the dimer? The bonds in E4 are
longer than in E2. As illustrated in section 7.2, the equilibrium
bond length in N2 is determined by the Pauli repulsion and not
by the maximum overlap of the orbitals. Each nitrogen atom in
N4 encounters Pauli repulsion from three other atoms, but only
from one atom in N2. The same holds for the phosphorus
systems, but the Pauli repulsion in P2 has a different gradient
than in N2 with respect to the interatomic distance. Pauli
repulsion appears between electrons of the same spin, and the
similar radii of the 2s and 2p AOs of nitrogen induce strong Pauli
repulsion at the equilibrium distance of N2, which sharply
increases at shorter distances. The Pauli repulsion in P2 at
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Figure 26. (a) and (b) Schematic representation of electronic 3B1 and 1A1 states of EX2. Schematic representation of the orbital interactions and
bonding models in various isomers of E2X4. (c) Electron-sharing σ and π bonding in planar E2X4 (model A). (d) Lone-pair donation in lp-bridged
structures E2X4 (model B). (e) Lone-pair donation in lp-bridged structures E2X4 (model C). (f) Bond pair donation in E-X-bridged structures E2X4
(model D).
equilibrium is weaker and increases less steeply, because the
singly occupied 3p AOs have a larger radius than the doubly
occupied 3s AO. This is shown in Figure 25, which displays the
energy terms of the EDA calculations of N2 and P2. The
interaction of one nitrogen atom with three N in N4 induces
stronger Pauli repulsion than the interaction of one P with the
other three phosphorus atoms in P4. This is the reason why the
N−N bonds in tetrahedral N4 are stretched by 32.8% relative to
N2 whereas the P−P bonds in the tetramer are stretched by only
16.2% compared to P2. The driving force for the particularly long
and weak N−N bonds in N4 is thus the Pauli repulsion, which is
due to the similar s/p ratio of the valence AOs.
The following conclusions arise from this section:
• The frequently made statement that π bonds between
heavier main-group atoms are particularly weak is not
justified. The relative contribution of π orbital interaction
to covalent bonding in heavier main-group compounds is
even larger than in molecules of the first octal row.
• The difficulty to isolate molecules of the heavier main-
group atoms with multiple bonds is not due to weak π
bonding. It is rather caused by the change of both the σ
and π bond strength in addition reactions where π bonds
are converted to σ bonds. P4 (Td) is significantly more
stable than 2 P2, but N4 (Td) is much higher in energy than
2 N2. This is mainly due to the very long and weak N−N
bonds in N4 (Td), which are caused by the strong Pauli
repulsion that originates from the similar size of the 2s and
2p orbitals.
7.4.5. Multiple Bonds of Heavy Main-Group Atoms:
X2CCX2 vs X2EEX2 (E = Si − Pb; X = H, F). The history of
experimental attempts to synthesize compounds that are heavier
group-14 homologues of alkenes and alkynes is a fascinating
chapter of chemical research. The various approaches, which
finally suceeded in an albeit unexpected way, have been
described in several review articles.269−297 They shall not be
discussed in this account, which focuses on the nature of
chemical bonding. Experiments showed that heavy alkene
species X2EEX2 (E = Si − Pb) possess nonplanar equilibrium
structures that are significantly different from the planar D2h
arrangement of ethylene.269 Similarly, the experimentally
observed geometries of the heavier alkyne compounds XEEX
8817
Review
possess strongly bent nonlinear geometries.270 The latter aspect
is discussed in the following section. Here we investigate the
bonding situation in the parent systems H2EEH2 (E = Si − Pb)
and in the fluorine compounds F2EEF2. Deviations of the
geometries of compounds R2EER2, where R is a bulky group, are
caused by steric effects. We focus on the underlying electronic
differences between the carbon−carbon bond in ethylene and
the E−E bonds in the heavier homologues.
The key for understanding the different E-E bonding and the
resulting equilibrium structures of X2EEX2 between carbon and
the heavier group-14 atoms was provided 30 years ago by
Trinquier and Malrieu298,299 and by Carter and Goddard,300
who suggested that the electronic states of the EX2 fragments are
crucial for the nature of the E−E bond.301 Figure 26a shows
schematically the (3B1) triplet state and Figure 26b the (1A1)
singlet state of EX2 and their relative energies. Methylene CH2
has a triplet ground state, which is perfectly suited to build an
electron-sharing double bond X2EEX2 (model A) consisting
of a σ and a π bond (Figure 26c). CF2 and the heavier EH2 and
EF2 species have a singlet (1A1) ground state, and they must be
formally exited to the triplet (3B1) state in order to engage in
electron-sharing bonding. Some ylidenes EH2 and EF2 with E =
Si−Pb bind through their singlet (1A1) ground state via donor−
acceptor interactions (model B) where the lone-pair
electrons of E interact with the vacant p(π) orbital of the other
fragment as shown in Figure 26d. This leads to nonplanar C2h
structures of the respective X2EEX2 molecules where atom E has
a pyrimidal ligand arrangement. This is a straightforward
explanation for the experimentally observed and calculated
nonplanar geometries of many heavier group-14 homologues of
alkenes. Model C refers to a hypothetical situation with mutual
dative bonds in a planar structure X2EEX2. It is used for the
discussion of electron-sharing and dative bonding in C2H4 and
C2F4 in section 8.
There is an alternative method of dative bonding
between EX2 fragments in their (1A1) singlet state where the
donation occurs from the E−X bonding orbital rather than the
lone-pair electrons of E. This is shown in Figure 26e (model D).
Textbook knowledge suggests that lone-pair electrons are
energetically higher lying and are therefore better donors than
bonding electrons, but this is strictly valid only for atoms of the
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Figure 27. Calculated geometries and relative energies of E2H4 and E2F4 isomers (E = C−Pb) at BP86/def2-TZVPP. Number of imaginary frequencies
i. Bond lengths in Å, angles in deg, energies in kcal/mol. The red numbers indicate the lowest energy structures.

Table 16. Calculated Bond Dissociation Energies De of Planar X2EEX2 into 2 EX2 in the 3B1 Triplet State and (in Parentheses)
BDE of the Lowest Energy Structure of E2X4 to 2 EX2 in the 1A1 Singlet Statea
E2H4 E2F4
De ΔE(S→T) De − 2ΔE(S→T) De ΔE(S→T) De − 2ΔE(S→T)
C 178.7 (210.3)c −15.8b 178.7 176.7 (74.3)c 51.2 (74.3)
Si 100.0 (67.8)c 16.5 67.0 111.5 (8.3)c 69.7 −27.9
Ge 93.7 (51.3)c 23.3 47.1 91.0 (18.8)c 81.5 −72.0
Sn 74.4 (40.5)c 27.3 19.8 65.9 (31.9)c 80.2 −94.5
Pb 60.4 (38.5)c 35.5 −10.6 -d (37.8)c 89.9 -
a
Excitation energies ΔE(S → T) of EX2 at BP86/def2-TZVPP. All values in kcal/mol. bThe triplet state is the ground state. cDissociation energy of
the lowest energy structure of E2X4 to 2 EX2 in the singlet state. dPlanar Pb2F4 dissociates during the geometry optimization into 2 PbF2.

first octal row. As mentioned above, the (n)p AOs of higher
main-group atoms have larger radii than the respective (n)s AO,
which leads to an increasingly higher %p character of the heavier
atoms in their bonding orbitals. As a consequence, the lone-pair
orbitals of the heavier atoms have a higher %s character which
lowers their energy. At some point the lone-pair orbitals are lower
in energy and less prone to charge donation than the bonding electron
pairs of E−X bonds. This is the reason why many low-valent main-
group compounds of the heavier elements possess bridging structures.
The rich and seemingly exotic chemistry of the cluster
compounds of the heavier main group elements is also based
on the stronger donor capabilities of the bonding orbitals than of
the lone pairs. This is elaborated and discussed in the paper by
Dehnen and co-workers in this issue.302
Figure 27 shows the calculated geometries and the relative
energies of the planar D2h form of E2X4 (E = C−Pb), which are
not energy minima, and the isomeric equilibrium structures with
trans-bent geometry and doubly X-bridging isomers, all of C2h
symmetry. The most stable isomer of the E2H4 compounds for E
= Si, Ge is the trans-bent form whereas the hydrogen-bridged
trans isomer is the energetically lowest lying species for E = Sn,
Pb. The most stable isomer for E2F4 is the trans-bent form for E
= Si and the F-bridged isomer for E = Ge, Sn, Pb. There are also
cis isomers of the bent structures and the bridged forms of E2X4,
which are slightly higher in energy than the respective trans
isomers. They are not discussed here, because their bonding
situation is similar to those in the trans isomers. The stability
8818
order suggests that the E−X bonds become better donors than
the lone-pair electrons for heavier E and that the turning point
depends on the nature of X. This occurs in the case of E2F4
already for the germanium system, because fluorine is more
electronegative than hydrogen. This leads to a higher %s
character of the lone-pair orbitals.
The strength of the electron-sharing double bonds X2EEX2
in the hypothetical planar forms of the molecules may be
estimated from the calculated bond dissociation energies De of
the reaction X2EEX2 (D2h) → 2 EX2 (3B1), which refers to EX2
in the electronic reference state. The comparison with the BDEs
of the most stable nonplanar structures reveals the different
stabilization energies that come from electron-sharing and
donor−acceptor interactions. Table 16 gives the computed data
together with the singlet−triplet excitation energies. Subtracting
the requested promotion energies ΔE(S → T) for obtaining the
3
B1 state of EX2 from the De values indicates the net stabilization
of the electron-sharing interactions. It becomes obvious that the
energy preference for the nonplanar structures of Si2H4 and
Ge2H4 surpasses only slightly the stronger electron-sharing
bonding in the planar forms, which requires excitation to the 3B1
state of EH2. The difference of the binding interactions becomes
much larger for Sn2H4 and Pb2H4, where the dative bonding in
the lowest lying trans-bridged form occurs via E-H donation.
The situation in fluorine-substituted systems E2F4 reveals
significant differences to the E2H4 compounds. The BDE of
planar C2F4 (74.3 kcal/mol), which is even less than the
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calculated BDE of the F−F single bond in C2F6 (87.3 kcal/ The comparison of the EDA-NOCV results for the lp-bridged
mol),237 is much smaller than the intrinsic interaction energy form of Sn2H4(B) with the H-bridged isomer Sn2H4(C) reveals
(176.7 kcal/mol) due to the rather large ΔE(S → T) value for the origin of the change in the relative energy of the two isomers.
CF2 (51.2 kcal/mol). The bonding situation in C2F4 and the The lp-bridged form Sn2H4(B) encounters identical Pauli
change in the electronic structure during bond rupture are repulsion and stronger electrostatic attraction than Sn2H4(C)
discussed in the section on dative bonding below. The electron- (Table 17). However, the orbital interactions in Sn2H4(C) are
sharing interactions in the planar structures of the heavier stronger than in Sn2H4(B), and they overcompensate the former
systems E2F4 have a similar magnitude as in the respective two effects. Thus, the EDA-NOCV results suggest that the
hydrogen systems E2H4, but the singlet → triplet excitation higher stability of Sn2H4(C) compared with Sn2H4(B) is due to
energies of EF2 are much higher than for EH2. This makes the the stronger charge donation of the Sn−H bonding orbital than
planar structures of the former much less stable than the bridged the lone-pair MO. The orbital interactions in Sn2H4(C) also
species. As mentioned above, the E−X bonds at some point comprise two major components ΔEorb(1) and ΔEorb(2), which
become stronger donors than the lone-pair orbitals. The gradual are the (+,+) and the (+,−) combinations of the Sn−H donor
change of the relative strength of the two types of interactions orbitals. This becomes obvious by inspection of the associated
can be monitored by EDA-NOCV calculations. deformation densities, which are displayed in Figure 28b. The
Table 17 shows the numerical results of the EDA-NOCV shape of Δρ and the connected HOMO and LUMO orbitals
calculations of the energetically lowest lying bridged isomers of show that the (+,+) combination of the Sn−H donor orbitals
provides, in this case, more stabilization than the (+,−)
Table 17. EDA-NOCV Results of the Most Stable Structures combination.
of E2H4 at BP86-D3/TZ2P+//BP86/def2-TZVPP The fluorine-bridged compounds differ significantly from the
hydrogen-bridged molecules, because fluorine carries lone-pair
Lp Lp Lp-
bridged bridged bridged H-bridged H-bridged electrons. Table 18 shows the EDA-NOCV results for the
(C2h) (C2h) (C2h) (C2h) (C2h) energetically lowest lying bridged isomers of E2F4. The turning
Isomer Si2H4(B) Ge2H4(B) Sn2H4(B) Sn2H4(C) Pb2H4(C) point from lp-bridging to more favorable F-bridging occurs
2 SiH2 2 GeH2 2 SnH2 2 SnH2 2 PbH2 already for E = Ge. The stabilizing interaction energy in the F-
fragments (1A1) (1A1) (1A1) (1A1) (1A1)
bridged isomer Ge2F4(C) is substantially larger (ΔEint = −41.7
ΔEint −81.3 −60.5 −40.7 −49.5 −48.0 kcal/mol) than in the lp-bridged species Ge2F4(B), which is
ΔEPauli 294.8 202.6 124.3 124.3 125.4 barely stabilized (ΔEint = −2.3 kcal/mol). Table 18 shows that
ΔEdisp −3.3 −2.8 −3.2 −3.7 −3.9 the Pauli repulsion in Ge2F4(C) is much larger than in
ΔEelstata −181.2 −138.2 −89.2 −86.1 −91.7 Ge2F4(B), but the electrostatic stabilization and the stronger
(48.6%) (53.1%) (55.2%) (50.6%) (54.1%)
orbital interaction compensate for the increase of ΔEPauli. The
ΔEorba −191.6 −122.2 −72.5 −84.1 −77.8
(51.4%) (46.9%) (44.8%) (49.4%) (45.9%) largest contribution to the orbital interactions comes from the
ΔEorb(1)b −149.9 −81.0 −39.8 −47.4 −45.2 donation of the σ lone-pair MOs of the bridging fluorine (Figure
(78.2%) (66.3%) (54.8%) (56.4%) (58.1%) 29a). There are several smaller orbital contributions, which are
ΔEorb(2)b −37.6 −36.8 −29.3 −26.8 −25.1 associated with a significant polarization of the electronic charge.
(19.6%) (30.1%) (40.5%) (31.9%) (32.3%)
This becomes visible by inspection of the deformation density
ΔEorb(rest)b −4.2 −4.4 −3.4 −9.9 −7.5
(2.2%) (3.6%) (4.7%) (11.7%) (9.7%) Δρ2 (Figure 29b). The red area of charge depletion is localized,
ΔEprep 14.1 9.7 4.7 5.5 5.3 but the blue area of charge accumulation is distributed over the
-De −67.2 −50.8 −35.9 −44.0 −42.6 whole molecule.
a 7.4.6. Multiple Bonds of Heavy Main-Group Atoms:
The values in parentheses give the percentage contribution to the
total attractive interactions ΔEelstat + ΔEorb. bThe values in HCCH vs HEEH (E = Si − Pb). The peculiar equilibrium
parentheses give the percentage contribution to the total orbital structures of the heavier group-14 homologues of actylene can
interactions ΔEorb. be explained in the same fashion as the nonplanar bridged
homologues of ethylene. Since the structures and bonding
situation in E2H2 (E = Si − Pb) have been discussed in recent
review articles,261,303 only the essential points are presented
E2H4. The tin compound Sn2H4 is the turning point where the here. More details can be found there and in the original
H-bridged form C becomes lower in energy than the lp-bridged work.304 Figure 30 summarizes the most important features of
isomer B (Figure 27). Therefore, we present for comparison the the E2H2 species.
results for both species Sn2H4(B) and Sn2H4(C). The calculated The nonplanar doubly hydrogen-bridged structure A is the
energy terms for the lp-bridged isomers B of E2H4 (E = Si − Sn) global energy minimum for all E2H2 molecules. The next
suggest that the attractive E−E interactions arise with similar energetically stable isomer is the singly bridged form B, which
strength from electrostatic forces and from orbital interactions. exhibits a peculiar inward bending of the terminal hydrogen
The ΔEorb term has two major components, which contribute atom. Species B has all three atoms on the same side of the triply
>95% to the dative bonding. Figure 28a shows the deformation coordinated atom E. This is a highly unusual bonding situation
densities Δρ of Sn2H4, which are associated with the individual for a group-14 atom. Both E2H2 isomers A and B have been
orbital interaction. The strongest contribution ΔEorb(1) comes observed for all elements E = Si − Pb in low-temperature matrix
from the mutual donation of the (+,−) combination of the lone- studies.305−310 The vinylidene species C is the next energetically
pair orbitals whereas ΔEorb(2) is due to the charge donation from higher isomer. It is the only energy minimum structure that is
the (+,+) lp combination. The associated interacting orbitals common for carbon and the heavier group-14 atoms Si−Pb.
HOMO and LUMO are also shown. It becomes obvious that the Finally, there are two trans-bent structures D1 and D2, which
interfragment interactions lead also to a significant charge possess significantly different E−E bond lengths and E−E−H
alteration (polarization) at each fragment. angles. Substituted homologues E2R2 with bulky groups R
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Figure 28. Plot of deformation densities Δρ (isovalue = 0.005) of the pairwise orbital interactions ΔEorb(1) and ΔEorb(2) and the associated fragments
orbitals in the (a) Lp-bridged isomer of Sn2H4 and (b) H-bridged structure of Sn2H4. The energy values are given in kcal/mol. The direction of the
charge flow is red → blue.

Table 18. EDA-NOCV Results of the Most Stable Structures EH requires formally the a4Σ− excited state of EH for the
of E2F4 at BP86-D3/TZ2P+//BP86/def2-TZVPP formation of an electron-sharing triple bond. The excitation
energy X2Π → a4Σ− of the heavier EH species is significantly
Lp Lp-
bridged bridged F-bridged F-bridged F-bridged larger than for CH. Table 19 shows the calculated bond
(C2h) (C2h) (C2h) (C2h) (C2h) dissociation energies De of the linear structures HEEH
Isomer Si2F4(B) Ge2F4(B) Ge2F4(C) Sn2F4(C) Pb2F4(C) yielding (a4Σ−) EH. Subtracting the excitation energies for two
2 SiF2 2 GeF2 2 GeF2 2 SnF2 2 PbF2 EH fragments to the a4Σ− state ΔEexc from the De values gives
fragments (1A1) (1A1) (1A1) (1A1) (1A1)
the net stabilization energy of the electron-sharing triple bond.
ΔEint −9.7 −2.3 −41.7 −49.7 −53.3 This value of 240.0 kcal/mol for CH is rather high; it clearly
ΔEPauli 68.6 21.7 161.7 135.4 113.6 surpasses the stabilization of an electron-sharing single bond,
ΔEdisp −3.4 −2.9 −3.3 −3.9 −4.2 which could be provided by coupling the unpaired electrons of
ΔEelstata −29.4 −5.0 −112.0 −109.6 −99.4 the EH fragments in the X2Π ground state. The net stabilization
(39.3%) (23.8%) (56.0%) (60.5%) (61.1%)
ΔEorba −45.5 −16.1 −88.0 −71.6 −63.3
energy De − 2ΔEexc for Si and Ge is much smaller (Table 19). It
(60.7%) (76.2%) (44.0%) (39.5%) (38.9%) does not compensate for the energy gain of a E−E single bond.
ΔEorb(1)b −26.0 −11.1 −52.0 −39.5 −34.9 The excitation energies of two SnH and PbH fragments are even
(57.3%) (69.3%) (59.0%) (55.2%) (55.1%) higher than the bond dissociation energy of linear HEEH. It
ΔEorb(2)b −17.9 −4.2 −13.7 −11.1 −10.1 follows that the bonding interactions between two EH species
(39.4%) (26.2%) (15.6%) (15.5%) (15.9%)
for E = Si − Pb occur from the X2Π ground state. The isomer C
ΔEorb(rest)b −1.5 −0.7 −22.3 −21.0 −18.3
(3.4%) (4.5%) (25.4%) (29.3%) (29.0%) is not considered, because it has a different atomic connectivity
ΔEprep 0.3 0.2 20.3 14.7 12.1 than the other species.
−De −9.4 −2.1 −21.4 −35.0 −41.1 Figure 32 shows three possible arrangements of the EH
a fragments in their X2Π ground state where the unpaired
The values in parentheses give the percentage contribution to the
total attractive interactions ΔEelstat + ΔEorb. bThe values in electrons are coupled to an electron-sharing σ bond. The
parentheses give the percentage contribution to the total orbital assignments (a) and (c) are unfavorable, because they leave the
interactions ΔEorb. unoccupied p(π) orbitals in the resulting species vacant.
Consequently, the structures are not energy minima but
transition states (i = 1). The arrangement (c) leads to structure
featuring D1 have been synthesized and structurally charac- D2, which becomes an energy minimum for E = Pb when bulky
terized for E = Si, Ge, Sn.311−314 The lead analogue Pb2R2 substituents prevent the formation of the electronically more
exhibits structure D2.315 The linear form E is an energetically favored isomers.316 The arrangement (b) in Figure 32 places the
high lying second order saddle point (number of imaginary EH bonds in perfect position to donate the associated electron
frquencies i = 2) for all heavy group-14 species E2H2. pairs into the respectively vacant p(π) orbitals. This leads to the
Figure 31 schematically shows the X2Π ground and the a4Σ− global energy minimum form A of the heavier E2H2 molecules. It
excited state of EH. It is obvious that the linear structure HE becomes clear that the structure A has a triple bond, which
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Figure 29. Plot of deformation densities Δρ (isovalue = 0.005) of the pairwise orbital interactions ΔEorb(1) and ΔEorb(2) and the associated fragments
orbitals in the (a) Lp-bridged isomer of Ge2F4 and (b) F-bridged structure of Ge2F4. The energy values are given in kcal/mol. The direction of the
charge flow is red → blue.
consists of one electron-sharing σ component and a degenerate
EH donor component.
Figure 33 shows three different placements of the (X2Π) EH
fragments where the unpaired electrons yield a π bond.
Placement (a) shows that the electron-sharing π bond is
supported by a lone-pair donor bond and a EH donor bond. The
optimal EH donation requires a tilting of the vacant p(π) orbital
of the right EH fragment, which leads to the inward bending of
the associated E−H bond. The formation of the EH donor bond
nicely explains the unusual equilibrium structure of the isomer
B, which has a triple bond that includes an electron-sharing π
bond, a lone-pair donor bond, and a EH donor bond. Rotation of
one EH fragment leads to structure G, which is not an energy
minimum, although it is lower in energy than B. Structure G
possesses two EH donor bonds, which are stronger than one EH
and one lone-pair donor bond in B. But G is the transition state
for the degenerate flip−flap rearrangement of the global energy
minimum A. Finally, there is the energetically highest lying
energy minimum D1, which has a triple bond consisting of an
electron-sharing π bond and two lone-pair donor bonds.
Substitution of hydrogen by bulky groups in E2H2 stabilizes
D1 so much that it can be isolated. When E = Pb, the isomeric
form D2 becomes lower in energy than D1, because the
electron-sharing π bond is replaced by a stronger σ bond and the
lone-pair donation of lead is rather weak.
The model presented here straightforwardly explains the
experimentally observed structures of E2H2, which possess
equilibrium geometries that are not directly accessible by the
Lewis bonding model. They can be straightforwardly explained
with an extension of the model by Trinquier and Malrieu298,299
and by Carter and Goddard,300 that was suggested for heavier
homologues of ethylene. With the information that is gained
from the analysis of the orbital interactions in E2H2 it is possible
to display the bonding situation in the isomers in terms of
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modified Lewis type structures for the isomers A, B, D1, and D2
as shown in Figure 34. It turns out that the Lewis model should
not be discarded or replaced, but it should be used in
conjunction with quantum chemical calculations.
The following conclusions arise from these sections:
• The nonplanar equilibrium geometries of the heavier
ethylene homologues E2X4 (E = Si − Pb) can be
understood in terms of dative interactions between
ylidene fragments EX2 in the electronic (X1A1) ground
state. The excitation energy from the (X1A1) ground state
to the 3B1 excited state is too high to make the planar
species with electron-sharing double bonds X2EEX2
energy minima.
• The dative bonds in E2X4 can be formed either via the
lone-pair electrons or by the E−X bond pairs as donors,
which become favorable when E is a heavier atom. The
turning point from lone-pair donation to E−X donation
depends also on the nature of X.
• The unusual equilibrium structures of the heavier
acetylene homologues E2H2 (E = Si − Pb) can be
explained analogously to the heavier ethylene systems
with the interaction of the EH fragments in the (2Π)
doublet ground state. The E−E bonds in the lowest lying
energy minima A, B, and D1 possess electron-sharing σ or
π single bonds, which are completed by lone-pair or E−H
dative bonds.
• The trans-bent equilibrium geometries of the isolated
systems E2R2 are enforced by steric repulsion of the bulky
groups R. In the case of E = Si, Ge, Sn, they have the
structure D1 with a triple bond whereas Pb2R2 features
structure D2 with a single bond.
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Figure 30. Optimized structures of E2H2 isomers A−E at BP86/QZ4P. Bond lengths are given in Å, angles in deg. The values for Θ give for structure A
the dihedral angle between the E2H and E2H′ planes. The relative energies with respect to A are given at the bottom of each entry in kcal/mol together
with the number of imaginary frequencies i. Reproduced from ref 304. Copyright 2005 American Chemical Society.

8. DATIVE BONDING IN MAIN-GROUP COMPOUNDS
In the examples of chemical bonding that were discussed so far, a
distinction was often made between electron-sharing bonding
and dative bonding. As mentioned above, the concept of dative
bonding and the associated notation with an arrow A→B in
contrast to an electron-sharing bond A−B is quite old, but it was
neglected by the strong influence of Pauling on the general view
of chemical bonding in the following period. Arne Haaland was a
lonely caller in the desert when he published a review article on
donor−acceptor interactions in main-group chemistry in
1989.48 It received little attention, which is probably due to
the fact that the work was restricted to well-known standard
molecules. The model of dative bonding was revived in the past
8822
decade following the suggestion that the chemical bonds and the
reactivity of carbodiphosphorane C(PPh3)2 can best be
understood in terms of donor−acceptor interactions Ph3P→
C←PPh3.50 The proposal not only led to an understanding of
the sometimes unusual geometries of related molecules such as
the bent equilibrium geometry of carbon suboxid C(CO)2;52,53
it was also the starting point for the synthesis of new molecules
with uncommon features.49,55,56 The term “carbone” was
suggested for divalent carbon(0) compounds CL2, which exhibit
a distinctly different chemical behavior than the carbenes CR2,
which are carbon(II) compounds.54 Carbones possess two lone
electron pairs whereas carbenes have only one. A particular class
of carbones CL2 are carbodicarbenes C(NHC)2, which possess
carbon−carbon dative bonds (NHC)→C←(NHC). Carbodi-
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Figure 31. Schematic representation of the electron configuration of
the 2Π electronic ground state and the a4Σ− excited state of EH (E = C
− Pb). The experimental24 and calculated (BP86/QZ4P) excitation
energies are given in kcal/mol.
Table 19. Calculated Bond Dissociation Energies De (kcal/
mol) of Linear HEEH → 2 EH (a4Σ−) and X2Π → a4Σ−
Excitation Energies ΔEexc (kcal/mol) of EH at BP86/QZ4P
E De ΔEexc De − 2xΔEexc
C 270.9 15.44 240.0
Si 121.6 38.56 44.5
Ge 113.3 47.09 19.0
Sn 89.4 45.87 −2.3
Pb 69.0 52.01 −35.0
carbenes were theoretically predicted as stable compounds in
2007,51 and they were synthesized for the first time in
2008.317,318 It was recently found that carbodicarbenes may be
used as catalysts in a variety of reactions, which are a topic of
intense experimental investigations.319−324
Following the discovery of carbones, heavier group-14
homologues EL2 (E = Si − Pb) were proposed as synthetically
achievable targets.325,326 Stable silylones SiL2, germylones GeL2,
and stannylones SnL2 have been isolated in the mean-
time.327−329 Perhaps the most amazing outcome of the carbone
model CL2 was the synthesis of the isoelectronic borylene
complex (BH)L2 with L = CAAC, which has a three-coordinated
boron atom that possesses an electron pair CAAC→(BH)←
CAAC.330 Substituted homologues (BR)L2 with different
ligands L have also been isolated in the meantime, of which
the dicarbonyl complex (BR)(CO)2 is the most surprising
example.331,332 It is the first stable dicarbonyl complex of boron
and the only dicarbonyl complex of any main-group atom
besides carbon suboxide C(CO)2 and the isoelectronic
nitronium cation N+(CO)2.333 The examples demonstrate the
value of a bonding model, which is based on a quantum chemical
analysis of the electronic structure of the molecules. Figure 35
gives an overview of the calculated and experimental structures
of carbones CL2 and isoelectronic boron and nitrogen
homologues (BH)L2 and N+L2 with various ligands. The trend
in the bond angles can be explained with the relative strength of
the π backdonation from the ligands to the central atom.49,58
The model of dative bonding is not only useful as a means of
interpretation of the bonding situation and as predictive
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guidance for synthesizing one-center complexes EL2, it can
also be applied to multicenter complexes. Several examples
where diatomic species E2 are stabilized by ligands L in stable
complexes L→E2←L have been discussed in section 7.3 above.
The basic principle of the stabilizing interactions in the two-
center adducts E2L2 is the same as in the one-center complexes
EL2.49 The mono- or diatomic fragment E or E2 is formally
excited to an electronic reference state, which is usually an
excited state and which makes the fragment a good acceptor.
The dative interactions L→En←L are strong enough to stabilize
the complex so it can be experimentally observed or even
isolated in bulk form. Recently, the concept was extended to
systems with triatomic cyclic systems E3L3 (Figure 36). The
triatomic Si(0) cluster Si3(CAAC)3, which has three Si⇆CAAC
donor−acceptor bonds, could be isolated and structurally
characterized by X-ray analysis.334 The triboron complexes
[B3(NN) 3] + and [B 3(CO)3 ]+ have been observed and
spectroscopically identified in the gas phase.335 The molecules
feature the smallest π-aromatic system B3+, which is stabilized by
three dative bonds with the ligands N2 and CO.
The usefulness to distinguish between electron-sharing and
dative bonding for understanding and also explaining chemical
reactions can be demonstrated with a recent example, in which
very similar substrates led to completely different products.
Roesky and co-workers reported in 2009 that the reaction of
NHC with HSiCl3 leads to the synthesis of the complex NHC→
SiCl2 (A), which was the first ligand stabilized Si(II) compound
that was isolated and structurally characterized by X-ray analysis
(Reaction 25, Figure 37).336 In a subsequent work, the authors
reacted A with CAAC, which according to quantum chemical
calculations binds more strongly to SiCl2 than NHC.
Surprisingly, the reaction gave the compound (SiCl2)(CAAC)2
(B) where silicon is four-coordinated, rather than the expected
complex (CAAC)→SiCl2 via 1:1 ligand exchange (Reaction 26,
Figure 37)337 The calculations showed that the Si−C bonds in
(SiCl2)(CAAC)2 are significantly shorter than in (CAAC)→
SiCl2.
HSiCl3 + 2NHC → NHC→SiCl 2(A) + NHC(H+)(Cl−)
(25)
NHC→SiCl 2(A) + 3CAAC
→ (SiCl 2)(CAAC)2 (B) + NHC‐CAAC (26)
The unexpected formation of four-coordinated (SiCl2)-
(CAAC)2 rather than (CAAC)→SiCl2 can straightforwardly
be explained with the presence of Si−C electron-sharing bonds
in the former compound in contrast to the latter adduct, which
has a Si←C dative bond. The formation of electron-sharing Si−
C in (SiCl2)(CAAC)2 (B) requires open-shell fragments in the
electronic triplet state, which leaves one unpaired electron at
each CAAC ligand (Figure 37). According to Hund’s rule, the
overall electronic state of (SiCl2)(CAAC)2 should be a triplet.
The EPR spectrum actually suggests a triplet state for the
compound. Interestingly, compound B possesses two poly-
morphic forms, where only one exhibits the EPR spectrum.337 It
appears that the unpaired electrons in one isomer are weakly
coupled via intermolecular interactions, making it diamagnetic.
There remains the question why SiCl2 binds two CAAC ligands
with covalent bonds while it only binds one NHC ligand with a
dative bond. The associated energies of bond formation and
electronic excitation provide a straightforward answer.
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Figure 32. Qualitative model for the orbital interactions between two EH molecules in different orientations where the unpaired electrons yield a σ
bond. Reproduced from ref 304. Copyright 2005 American Chemical Society.
Figure 33. Qualitative model for the orbital interactions between two
EH molecules in different orientations where the unpaired electrons
yield a π bond. Reproduced from ref 304. Copyright 2005 American
Chemical Society.
Figure 37 gives the calculated bond dissociation energies of
the mono and bis adducts of SiCl2 with NHC and CAAC ligands
and the singlet → triplet excitation energies.337 The bottom end
shows the energy balance for electron-sharing bonding of SiCl2
with NHC and CAAC. The sum of energy gained due to bond
formation and singlet → triplet excitation energies for the CAAC
ligand results in a net stabilization of 67.3 kcal/mol for
(SiCl2)(CAAC)2, which surpasses the BDE of (SiCl2)(CAAC)
(42.5 kcal/mol). In contrast, the formation of (SiCl2)(NHC)2
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Figure 34. Suggested Lewis structures for isomers A, B, D1, and D2 of
E2H2 isomers.
gives only a net stabilization of 7.3 kcal/mol, because the singlet
→ triplet excitation energy of NHC (88.9 kcal(mol) is much
higher than for CAAC (49.9 kcal/mol). The energies calculated
on the basis of the two bond types provide not only an
explanation for the experimental observation. They serve also as
a guideline for predicting the experimental outcome of further
reactions with different carbene ligands, which mainly depends
on the energy difference between their singlet and triplet state.
How can a dative bond, A→B, be distinguished from an
electron-sharing one, A−B? The question seems to be easily
answered by looking at the fragments that arise after breaking
the bond. Dative bonds tend to dissociate heterolytically while
electron-sharing bonds usually break up in a homolytic fashion.
However, the situation is more complicated, because the nature
of the bonding interactions may change during the bond
breaking process. A good example is the carbon−carbon double
bond F2CCF2, which is a classical electron-sharing bond that
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Figure 35. List of isoelectronic molecules EL2 with calculated bond angles and partial charges Δq of the central fragments E = BH, C, N+. Experimental
bond angles of isolated molecules are given in parentheses. Reproduced from ref 49. Copyright 2017 Elsevier.
consists of a σ and a π component. But the fragments, which are
eventually formed during the bond-breaking process, are two
CF2 species in the singlet (1A1) state. Since bond breaking is the
reverse process of bond formation, the initial interaction must
have a dative nature (see model B in Figure 26d). A different
situation exists for ethylene H2CCH2, because the interacting
methylene fragments have a triplet (3B1) ground state, which
straightforwardly leads to electron-sharing σ and π bonding in
the molecule (model A, Figure 26c). The different electronic
states of the carbene fragments have a drastic effect on the BDE
of the alkenes. Table 20 shows the calculated values of the
alkenes C2X4 and alkanes C2X6 (X = H, F). The De values for the
hydrogen bonded parent systems show the expected order; that
is, the H2CCH2 double bond is much stronger than the H3C−
CH3 single bond. In contrast, the F2CCF2 double bond is
weaker than the F3C−CF3 single bond, although the former
bond is even shorter than in H2CCH2. It becomes obvious
that the bond dissociation energy is not a reliable measure for
the strength of a chemical bond.
The carbon−carbon double bonds in H2CCH2 and F2C
CF2 have recently been studied in terms of dative and electron-
sharing bonds with the EDA-NOCV method.237 Table 21 gives
the numerical results of the calculations, where the carbene
fragments were arranged in the singlet and triplet states
according to bonding models A and C (Figures 26c and 26e).
It becomes obvious that the calculated interaction energies ΔEint
between the triplet fragments in H2CCH2 and F2CCF2 are
a more faithful description than the bond dissociation energies
De. The ΔEint values give the strength of the stabilizing
interactions in the eventually formed bond while the De values
for C2F4 include the electronic relaxation of the CF2 fragments
from the triplet to the singlet state.
The preference for describing the double bonds in terms of
electron-sharing interactions rather than dative bonds is
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revealed by the values of the orbital interactions ΔEorb values.
As mentioned above, those fragments, whose electronic energies
change least during the covalent bond formation, provide the
best description of the chemical bond. This criterion was used
for a variety of chemical bonds where the description in terms of
dative or electron-sharing interactions was not clear.133−146
Table 21 shows that the ΔEorb values using triplet fragments are
smaller than with singlet fragments for H2CCH2 and F2C
CF2, which supports the notion that also the latter compound
has an electron-sharing double bond. The change from electron-
sharing bonding at equilibrium to dative bonding during
carbon−carbon bond breaking can be monitored by EDA
calculations along the dissociation profile. Figure 38 shows the
calculated reaction pathway for the carbon−carbon bond
breaking/bond formation reaction of C2F4 at different levels of
theory.237 The calculations suggest a smooth reaction profile
where the CF2 fragments initially approach each other in a side-
way orientation. The molecule becomes planar only at the final
stadium of the bond formation. There is no activation barrier for
the reaction; the small hump at the CASSCF(8,8) level is due to
the lack of dynamic correlation.
Table 22 shows the calculated ΔEorb values at different C−C
distances using the singlet and triplet electronic states of CF2,
which refer to the three different bonding models A, B, and C.
The electron-sharing model A provides the best description for
shorter distances as suggested by the ΔEorb values, but for longer
distances the dative model B becomes better than A. Model C is
not relevant at any carbon−carbon distance. The trend of the
ΔEorb values shows that the change from electron-sharing to
dative bonding can be illustrated with the EDA-NOCV method.
It should be kept in mind that the transition involves a change of
the model and not a change in the nature of the interatomic
interactions.
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Figure 36. (a) Geometry and bonding situation of the isolated complex Si3(CAACR)3 with experimental and (in parentheses) calculated bond lengths
(Å) and angles (deg). Reprinted with permission from ref 334. Copyright 2016 John Wiley and Sons. (b) Calculated geometry and bonding situation of
the experimentally observed aromatic cations B3L3+ (L = CO, N2). Reprinted with permission from ref 335. Copyright 2016 John Wiley and Sons.
Finally, we would like to discuss three systems LX2L with
valence isoelectronic species X2 = N2, C2H2, and Si2H2, where
the dichotomy of dative and electron-sharing bonds is a
challenge for chemical intuition. Figure 39 shows three
molecules 1−3, which may be written in either of the two
depicted ways. Compound 1 (E = N) with a bz-NHCMe ligand
(bz-NHCMe denotes a benzoannelated NHCMe ligand with
methyl groups at nitrogen) was synthesized in 2012, where it was
termed as a guanidine compound, which was sketched with the
classical Lewis structure 1a.338 The above-described bonding
analysis of N2(PPh3)2, which was recognized as donor−acceptor
complex Ph3P→N2←PPh3, let it seem possible that compound
1 is better described with dative bonds bz-NHCMe→N2←bz-
NHCMe (1b). The choice of the bz-NHCMe ligands was made,
because the molecule was supposed to be compared with the
isoelectronic species C2H2(bz-NHCMe) (2), which was reported
to have some surprising chemical behavior.140 Very recently, the
silicon system 3 was reported, which may be considered as
ligand stabilized disilaacetylene complex 3b or as substituted
2,3-disilabutadiene 3a.136
Table 23 shows the results of the EDA-NOCV calculations of
1−3. The data suggest that the chemical bonds at the central N2
fragment in 1 are indeed better described in terms of dative
interactions bz-NHCMe→N2←bz-NHCMe (1b) than with
electron-sharing bonds (1a). The same conclusion is drawn
8826
Review
for compound 2, where the dative interactions bz-NHCMe→
C2H2←bz-NHCMe (2b) lead to a smaller ΔEorb value than the
electron-sharing model 2a, which refers to a tetraaminobuta-
diene. There is chemical evidence that 2b is indeed a more
faithful representation of the chemical bonds than 2a. When the
dication 22+ is reacted with silver or gold compounds, the in situ
generated 2 reacts and gives a major product the metal
complexes bz-[NHCMe→M←bz-NHCMe]+ (M = Ag, Au)
where the metal cation replaces the central C2H2 moiety.140
Such reaction is unknown for tetraaminobutadiene compounds.
The EDA-NOCV calculations for Si2H2(CAACDip) (Dip = 2,6-
diisopropylphenyl) suggest that the description in terms of
dative and electron-sharing bond have essentially equal weight.
Consequently, the synthesis of 3 was reported with the title “The
Structure of the Carbene Stabilized Si2H2 May Be Equally Well
Described with Coordinate Bonds as with Classical Double
Bond”.136
The following conclusions arise from this section:
• The distinction of the covalent electron-pair bonding into
electron-sharing and dative interactions is a helpful model
for understanding the structures and reactivities of
molecules. It is also a powerful tool for predicting stable
molecules with unusual chemical bonds.
• Dative bonds A→B usually tend to dissociate heterolyti-
cally and electron-sharing bonds A−B normally break up
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Figure 37. Reactions of SiCl2 with NHC and CAAC and schematic view of the bonding situation in the complex NHC→SiCl2 (A) and the molecule
SiCl2(CAAC)2 (B) in the triplet state. Below are the calculated bond dissociation energies at M05-2X/def2-TZVPP of the complexes SiCl2(NHC) and
SiCl2(CAAC) and the compounds in the triplet state SiCl2(NHC)2 and SiCl2(CAAC)2 as well as the singlet−triplet gaps of the fragments. The bottom
lines give the net stabilization energies ΔE for the formation of the electron-sharing bonds in SiCl2(NHC)2 and SiCl2(CAAC)2 in comparison with the
dative bond. Reprinted with permission from ref 337. Copyright 2013 John Wiley and Sons.

Table 20. Calculated (Experimental) C−C Bond Lengths Re Table 21. EDA Calculations of C2F4 and C2H4 at the M06-L/
[Å] and Calculated (Experimental) Bond Dissociation TZ2P Level Using Triplet and Singlet Fragments According
Energies De [kcal/mol]a to Models A and C (Figure 26)a
Re De C2F4 C2H4
H3CCH3 1.532 (1.522) 93.1 (89.7) Fragments Triplet (A) Singlet (C) Triplet (A) Singlet (C)
H2CCH2 1.333 (1.336) 178.2 (172.1) ΔEint −197.7 −279.9 −196.7 −278.1
F3CCF3 1.567 (1.545) 87.3 (96.4) ΔEMetaGGA 6.2 −4.8 7.9 7.6
F2CCF2 1.329 (1.311) 73.3 (70.3) ΔEPauli 305.0 292.9 291.4 282.8
a
Calculated values were obtained at the M06-L/TZ2P level of theory. ΔEelstatb −182.7 −175.6 −183.6 −181.2
Taken from ref 237. (35.9%) (30.9%) (37.0%) (31.9%)
ΔEorbb −326.1 −392.5 −312.4 −387.2
(64.1%) (69.1%) (63.0%) (68.1%)
homolytically, but the dissociation products are not
ΔEorb(σ)c −209.2 −221.5 −218.0 −241.2
always reliable probes for the type of the bonding. This is (64.2%) (56.4%) (69.8%) (62.3%)
because the nature of the interatomic interactions may ΔEorb(π)c −87.0 −142.0 −79.4 −129.9
strongly change during the bond formation in a way that (26.7%) (36.2%) (25.4%) (33.5%)
the initially dative interactions eventually turn into ΔEorb restc −29.9 (9.2%) −29.0 (7.4%) −15.0 (4.8%) −16.1 (4.2%)
electron-sharing bonding. ΔEprep 122.2 204.4 20.7 102.1
ΔE = −De −75.5 −75.5 −176.0 −176.0
• Dative and electron-sharing bonds are models, which are a
helpful tools for the description and prediction of the Energy values in kcal/mol. Taken from ref 237. bThe values in
structures and reactivities of molecules. There may be parentheses give the percentage contribution to the total attractive
cases where both descriptions have similar validity. interactions ΔEelstat + ΔEorb. cThe values in parentheses give the
percentage contribution to the total orbital interactions ΔEorb.

9. THE OCTET RULE AND THE ATOMIC VALENCE
SPACE OF MAIN-GROUP ATOMS
There is ample evidence that the atoms of groups 1, 2, and 13−
18 of the periodic system called main-group elements use only
their s and p valence orbitals for chemical bonding. Since the
exchange (Pauli) principle allows at most two electrons in one
orbitals, the four valence orbitals can accommodate a maximum
of eight electrons. This is the quantum theoretical basis for the
octet rule, which was suggested by Langmuir already in 1921.6
The extension of the valence space to d-orbitals, which was
8827
earlier suggested to explain the stabilty of so-called hypervalent
molecules, was discarded on the basis of quantum chemical
calculations. Atomic orbitals with higher angular momentum
such as d and f functions only serve as polarization functions for
the sp space, but they are not genuine valence orbitals in main-
group compounds.339,340 The evaluation of the symmetry of the
molecular orbitals shows that molecular wave functions may be
constructed that assign more than four bonds to an atom
although they only use its four atomic valence s and p functions
for chemical bonding. This has been discussed in section 7.4.
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Figure 38. Calculated reaction pathway for rupture of the carbon−

carbon bond of C2F4 with different theoretical methods. The energy is
given with respect to the dissociation product 2 CF2 (1A1). Reprinted
with permission from ref 237. Copyright 2018 John Wiley and Sons.

Recently, joint experimental/theoretical studies reported the
observation and identification of the earth alkaline carbonyl
complexes M(CO)8 (M = Ca, Sr, Ba) in low-temperature
matrices, which possess chemical bonds that are typical for
transition metals.102 The molecules fulfill the 18-electron rule,
and the metal−carbonyl bonds were explained with the Dewar−
Chatt−Duncanson (DCD) model1,341,342 in terms of M ← CO
σ donation and M → CO π backdonation. Surprisingly, the latter
interactions involve the valence d orbitals of the earth alkaline
atoms, which are vacant in the electronic ground state. The
electronic reference state of the metal atoms is the excited triplet
(3F) state with the electron configuration (n)s0(n−1)d2, which
is stabilized via strong M(d) → CO π backdonation. In a
forerunner of the work, the authors had found that the barium
carbonyl cation Ba(CO)+ exhibits a strong red shift of the C−O
stretching mode, which was explained with large Ba(5d)+ → CO
π backdonation.343 It is highly unusual that a cation serves as a
donor to a neutral species. The possible involvement of d
orbitals in barium compounds was earlier suggested by Pyykkö,
who coined the term “honorary transition metal” for barium.344
But it seems that transition metal-like bonding may not be
restricted to barium.
Figure 39. Schematic representation of alternative bonding situations
with dative or electron-sharing bonds for molecules with valence
isoelectronic fragments. (a) N2(bz-NHCMe)2; (b) (C2H2)(bz-
NHCMe)2; (c) (Si2H2)(CAACDip)2 (Dip = 2,6-diisopropylphenyl).
Figure 40 shows the calculated equilibrium geometries of
neutral M(CO)8 and the cations M(CO)8+ (M = Ca, Sr, Ba),
which were observed in the gas phase.102 The molecules were
identified by comparing experimental infrared spectra with
calculated wave numbers. The complexes are stable with respect
to loss of one CO ligand by 8.4−11.5 kal/mol. The neutral
species exhibit strong red shifts of the single IR active C−O
stretching mode by 130−160 cm−1. Also the cations show a red
shift by 30−50 cm−1, which can be explained with one and two
occupied d-orbitals in the cations and neutral molecules,
respectively. Figure 41 shows the correlation diagram of a
metal with a (n)s, (n)p, (n−1)d shell and eight CO in a cubic
(Oh) field. The qualitative model suggests that a total of 14
electrons are donated from the CO lone-pair MOs to the metal
into (a) the triply degenerate t2g (n−1)d-AOs, (b) the triply
degenerate t1u (n)p-AOs, and (c) the (n)s AO. One σ electron
pair of the ligand cage has a2u symmetry, which does not match

Table 22. Calculated EDA Values at M06-L/TZ2P of the Orbital Term ΔEorb [kcal/mol] for the Interactions between CF2 with
Different Electronic States and Different C−C Distances dC−C [Å]a

dC−C 1.30 1.326a 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.20 2.40 3.00
Model A
ΔEorb −339.5 −326.1 −290.9 −245.6 −217.3 −195.0 −178.4 −165.9 −156.5 −144.3 −137.7 −131.4
Model B
ΔEorb −856.4 −802.0 −665.8 −420.9 −275.1 −188.0 −133.3 −96.4 −70.4 −38.1 −20.7 −3.9
Model C
ΔEorb −406.0 −392.5 −357.1 −359.4 −365.5 −349.3 −326.1 −303.3 −283.7 −255.0 −237.1 −215.6

a
The bold values depict the smallest ΔEorb value at the respective C−C distance. Data taken from ref 237.

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Table 23. EDA-NOCV Calculations at the BP86-D3(BJ)/TZ2P Level of Theory of N2(bz-NHCMe)2, C2H2(bz-NHCMe)2, and
Si2H2(CAACDip)2 and Using the Interacting Fragments in the Singlet (S) or Quintet (Q) Electronic Statea
N2(bz-NHCMe)2 C2H2(bz-NHCMe)2 Si2H2(CAACDip)2
2 bz-NHCMe (S) Me
2 bz-NHC (Q) Me
2 bz-NHC (S) Me
2 bz-NHC (Q) Me
2 CAAC (S) 2 CAACMe (Q)
Fragments + N2 (S)c + N2 (Q) + C2H2 (S)c + C2H2 (Q) + Si2H2 (S)c + Si2H2 (Q)
Bonding dative electron-sharing Dative electron-sharing dative electron-sharing
ΔEint −393.5 −633.5 −465.3 −436.0 −193.0 −323.5
ΔEPauli 1275.3 1083.2 636.5 924.8 665.2 436.0
ΔEdisp −7.2 −7.2 −10.4 −10.4 −33.4 (3.9%) −33.4 (4.4%)
ΔEelstatb −547.8 (33.0%) −487.4 (28.5%) −385.4 (36.8%) −503.9 (37.3%) −423.9 (49.4%) −328.6 (43.3%)
ΔEorbb −1113.9 (67.0%) −1222.1 (71.5%) −706.1 (63.2%) −846.5 (62.7%) −401.0 (46.7%) −397.5 (52.3%)
a
Energy values are given in kcal/mol. The data are taken from refs 49, 136, and 140. bThe values in parentheses give the percentage contribution to
the total attractive interactions ΔEelstat + ΔEorb. cThe π and π* MOs in the electronically excited reference state are occupied.

Figure 40. Calculated equilibrium geometries of alkaline earth octacarbonyls. (A) M(CO)8 (M = Ca, Sr, or Ba), (B) [M(CO)8]+ (M = Ca or Sr), and
(C) [Ba(CO)8]+. Bond lengths are in angstroms. The D0 values in roman type are the ZPE-corrected bond dissociation energies for loss of one CO
ligand; the italicized values are the corresponding energies for the loss of eight CO ligands and M/M+ in the ground state. The values without
parentheses are from M06-2X-D3/def2-TZVPP calculations; the values in parentheses are from CCSD(T)/def2-TZVPP using M06-2X-D3/def2-
TZVPP optimized geometries. Reprinted with permission from ref 102. Copyright 2018 American Association for the Advancement of Science.

any valence orbital of the metal. The earth alkaline atoms have
therefore only 16-electrons in their valence shells. Although the
complexes are formally 18-electron species, they are effectively
16-electron complexes. The HOMO is a degenerate orbital, and
the molecules are therefore in agreement with Hund’s rule
triplets. The singly occupied MO of the cations induces due to
Jahn−Teller distortion a lower symmetry of the equilibrium
structure.
Table 24 shows the results of EDA-NOCV calculations on
M(CO)8, which give among others a quantitative account of the
individual orbital contributions that are sketched in Figure 41.
The data show that the most important valence orbitals of the
metals are the (n−1)d functions, which contribute 85%−95% to
the total orbital interactions. The dominant contribution is due
to the (n−1)d → (CO)8 π backdonation. Therefore, the alkaline
earth atoms calcium, strontium, and barium bind the CO ligands
in M(CO)8 like typical transition metals. The intrinsic
interaction energies ΔEint between the metal atoms in the
excited 3F state and the (CO)8 ligand cage is very strong; it
overcompensates the (n)s → (n−1)d excitation energies of the
metals. The bonding analysis of the recently reported 20-
electron systems M(CO)8− (M = Sc, Y, La), which also have
cubic (Oh) symmetry, showed a very similar bonding pattern.345
The HOMO in Figure 41 is fully occupied in the latter
compounds, which are thus effectively 18-electron complexes.
The above results indicate that some atoms of the sp shell are
able to use their d orbitals, which are empty in the electronic
ground state, for chemical bonds in stable molecules that are
8829
characteristic for transition metal compounds. The possible
extension of this concept to other atoms than the alkaline earth
elements and further ligands has yet to be explored. A guideline
for the search of other stable molecules is the excitation energy
from the occupied sp shell to the d orbitals and the strength of
the bonds to a ligand. This concept proved to be useful for
finding the class of carbones and related compounds, which are
mentioned in section 8. It might also be helpful for the search of
molecules where classical main-group atoms bind like transition
metals.
The following conclusions arise from this section:
• The valence space of the main group atoms usually
comprises the outermost s and p orbitals, which is the
basis for the octet rule. However, main-group elements
can also form stable molecules with covalent bonds using
their d-orbitals when the excitation energy to the d-shell is
compensated by the binding energies. This has recently
been demonstrated by the synthesis of the octacarbonyl
complexes M(CO)8 (M = Ca, Sr, Ba).
10. RELATIVISTIC EFFECTS IN MAIN-GROUP
COMPOUNDS
When one moves to the heaviest elements in the periodic table,
relativistic effects need to be considered in chemical bonding.
Since relativistic quantum theory is relatively a newcomer to the
field of quantum chemistry, and from the theoretical point of
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Figure 41. Bonding scheme and shape of the occupied valence orbitals of M(CO)8 (M = Ca, Sr, or Ba). Splitting of the spd valence orbitals of an atom
M with the configuration (n−1)d2(n)s0(n)p0 in the octacoordinate cubic (Oh) field of eight CO ligands is also given. Only the occupied valence orbitals
that are relevant for the M−CO interactions are shown. Up and down arrows indicate electrons with opposite spin. Reprinted with permission from ref
102. 2018 American Association for the Advancement of Science.
view quite demanding for chemists, we briefly outline the most
important qualitative view points of this field.
The Schrödinger equation is usually presented in quantum
chemistry in its time-independent form (eq 27). The kinetic
energy requests the second derivatives with regard to the spatial
coordinates (x,y,z). The time-dependent Schrödinger equation
(eq 28) involves the derivative with respect to the time
originating from the energy quantization, but the time
differential is only of first order. Relativistic theory demands
that time and space are equivalent coordinates in the four
dimensional space-time continuum, and thus, they must be
treated equally in physics. The Schrödinger equation is therefore
not compatible with relativity, but it naturally emerges from the
nonrelativistic limit (velocity of light c → ∞).
[−h2 /2m(∂ 2/∂x 2 + ∂ 2/∂y 2 + ∂ 2/∂z 2) + V (x , y , z)]
Ψ(x , y , z) = E Ψ(x , y , z) (27)
[−ℏ2 /2m(∂ 2/∂x 2 + ∂ 2/∂y 2 + ∂ 2/∂z 2) + V (x , y , z , t )]
Ψ(x , y , z , t )
= ih∂/∂t Ψ(x , y , z , t ) (28)
The problem to bring the Schrödinger equation in harmony
with special relativity was solved by Dirac. He introduced a (4 ×
4) matrix operator, which brings the spatial and time coordinates
on equal footing. Mathematical details on the Dirac operator D
shall not be presented in this work; they are discussed in several
review articles and monographs.346−354 The most important
result of the Dirac eq 29 is the manifestation of ΨD =
(ΨLαΨLßΨSαΨSß) being a four-component wave function
(spinor).
DΨD(x , y , z , t ) = E ΨD(x , y , z , t ) (29)
8830
Review
Loosely speaking, the two large components ΨLα and ΨLß of
the relativistic wave function ΨD refer to electrons with α and ß
spin, and the remaining two small components ΨSα and ΨSß are
required to allow for the existence of positrons (the antiparticles
of the electrons with the same mass and spin but opposite
charge), which were not yet known in 1928 when Dirac
developed his theory and whose existence was predicted by
him.355 Positrons were only identified in 1932.356 Thus, the
Dirac equation directly yields the electron (and positron) spin,
whereas spin (and its resulting spin−orbit coupling) must be
introduced ad-hoc into the nonrelativistic Schrödinger equation.
Calculations involving the Dirac equation with the full four-
component wave function ΨD are significantly more compli-
cated and demanding than those of the nonrelativistic
Schrödinger equation, mainly due to the fact of the appearing
negative energy continuum and increasing computational costs
of the matrix form of the Dirac operator. Nevertheless, a number
of four-component methods have been developed over the past
30 years, applicable routinely to smaller systems.357 For larger
systems, approximate two-component methods have been
developed, which involve the separation of the large from the
small component in the Dirac wave function and a trans-
formation to a two-component formalism.358−360 Two-
component methods such as the recently introduced X2C
approximation are less computer time-consuming than four-
component procedures but are still computationally expensive
especially when electron correlation is included.346−354,361,362
Therefore, the presently most commonly used quantum
chemical approaches including relativistic effects in chemistry
are based on one-component (scalar relativistic) approxima-
tions, such as the Douglas−Kroll method modified by Hess363 or
the Zeroth Order Regular Approximation (ZORA).364 A very
popular time-efficient and quite accurate alternative is the use of
relativistic effective core potentials (ECPs), also called
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Table 24. EDA-NOCV Results for Triplet State M(CO)8 (M This is because valence electrons can have substantial density in
= Ca, Sr, Ba) Complexes at the M06-2X/TZ2P-ZORA//M06- the core region where relativistic perturbation operators
2X-D3/def2-TZVPP Level Taking (CO)8 in Singlet Ground act.375,376 This gives rise to three major effects of relativity on
State and M in Triplet Excited State with a (n)s0(n−1)d2 the valence electrons, which are important for the electronic
Valence Electronic Configuration as Interacting Fragmentsa structure and bonding situation in molecules:368 (a) The lowest
lying s orbitals (and often p orbitals but to a lesser extend)
Ca + Sr + Ba +
Energy term (CO)8 (CO)8 (CO)8 stabilize and contract; that is, their shell radii become smaller
(direct relativistic effect). (b) Because of this direct relativistic
ΔEint −243.1 −224.1 −145.2
ΔEhybridb 41.8 46.9 37.4
effect the nucleus becomes more screened lowering the effective
ΔEPauli 19.5 30.5 30.8
nuclear charge for each orbital, and most notably the higher
ΔEelstatc −65.3 −61.7 −78.5
angular momentum (more diffuse) functions expand and the
(21.5%) (20.5%) (36.8%) orbital energies increase. This effect is called the indirect
ΔEorbc −239.1 −239.7 −135.0 relativistic ef fect and is more important for the d and higher
(78.5%) (79.5%) (63.2%) angular momenta shells. (c) The third effect is the coupling of
ΔEorb(1)d,e (eg) [M(d)]→(CO)8 π −206.2 −206.4 −95.0 the electron spin with its angular momentum. This effect is
backdonation (86.2%) (86.2%) (69.8%)
called spin−orbit coupling (correctly derived only from the Dirac
ΔEorb(2)d,e (t2g) [M(d)]←(CO)8 σ −21.3 −20.7 −22.8
donation (9.0%) (8.7%) (16.8%) equation), which, for example, leads to a splitting of the p
ΔEorb(3)d (a1g) [M(s)]←(CO)8 σ −2.4 −2.9 −3.2 orbitals into a p1/2 and p3/2 component. We note that the
donation (1.0%) (1.2%) (2.4%) contraction of the p1/2 component of the orbital is much larger
ΔEorb(4)d,e (t1u) [M(p)]←(CO)8 σ −0.9 −0.9 −2.7 than for the p3/2 component. Figure 42 shows the variation of the
donation (0.3%) (0.3%) (2.1%) orbitals under the influence of relativistic effects.377
ΔEorb(5)d (a2u) (CO)8 polarization −0.6 −1.0 −2.3 In many-electron systems the underlying shell structure has
(0.3%) (0.4%) (1.7%)
ΔEorb(rest)d −7.7 −7.8 −9.0
significant influence on the magnitude of relativistic effects.378
(3.2%) (3.3%) (6.7%) For example, in neutral Tl the 6p1/2 orbital contracts (−10.4%)
ΔEprep(a) 8 CO → (CO)8 13.9 7.7 3.3 while the 6p3/2 orbital expands slightly (+2.2%). Spin−orbit
ΔEprep(b)f M, (n)s2 → (n) 159.5 150.9 68.2 splitting in the p-levels can be substantial; for example, for the
s0(n−1)d2 (T) heavy p-block row we get for the spin−orbit splitting (in kcal/
ΔE (ΔEint + M(CO)8 → M (1S) −69.7 −65.5 −73.7 mol) in the spectroscopic levels379 of Tl 22.3 (2P1/2/2P3/2), Pb
ΔEprep) = −De + 8 CO
a
30.4 (3P0/3P2), Bi+ 48.7 (3P0/3P2), Po 48.1 (3P2/3P1) and At
Energy values are given in kcal/mol. bContribution of the 60.3 (2P3/2/2P1/2).380 It becomes obvious that such large energy
metahybrid term in M06-2X. cThe values within the parentheses differences due to relativity become manifest also in chemical
show the contribution to the total attractive interactions ΔEelstat +
bonding. Interestingly, subtle shell structure effects378 can lead
ΔEorb. dThe values within the parentheses show the contribution to
the total orbital interaction, ΔEorb. eThe sum of the two (eg) or three to a much larger percentage contraction of the valence s-orbital
(t2g, t1u) components is given. fThe EDA calculations give a triplet compared to the core−shell s-orbitals. For example, for the
state with spherically symmetrical distribution of the d electrons. The neutral atom Tl we get the following s-contractions/orbital
experimental values for excitation into the energetically lowest lying stabilizations:381 1s −12.7/10.7%, 2s −13.4/17.4%, 3s −10.6/
3
F state with (n)s0(n−1)d2 configuration are 124.2 and 59.8 kcal/mol 18.1%, 4s −9.4/20.1%, 5s −9.5/21.7%, 6s −13.1/24.4%.
for Ca and Ba. There is no experimental value for the relevant 3F state Moreover, relativistic effects in the s-levels of the p-block
of Sr. The data are taken from ref 102. elements are particularly large from filling the lower lying core d-
shell.382 This rather strong relativistic valence s-shell contraction
pseudopotentials.365,366 The basic idea behind the pseudopo- leads to a large separation between the ns/np levels and to a
tential approximation goes back to Hellmann, who introduced reduced mixing (hybridization) between the two, thus altering
the concept already in 1933.367 Here, the chemically inactive chemical bonding in the p-block heavy-element section
core electrons of the atom are replaced by an effective potential, substantially. This comes on top of the reduced s/p mixing
which is optimized in relativistic atomic calculations mimicing from the first to the second octal-row atoms discussed above.
the influence of relativistic effects on the valence electrons. Thus, Interestingly, these perhaps unexpected large relativistic effects
ECP calculations do not only consider relativistic effects but also and their consequence for chemical and physical properties have
reduce the number of electrons in quantum chemical been accepted far earlier by the chemistry than by the physics
calculations. Small-core ECPs explicitely retain the outer community.
core−electrons in the calculations, whereas the less accurate Spin−orbit effects can be large in heavy elements but are
large-core ECPs consider only the immediate valence shell. The suppressed in strong ligand fields, which is best described by
relativistic ECP approximation transfers relativistic effects ionic bonding models. This is obvious as we formally move
extremely well from the atomic into the molecular environment; electron density from orbitals undergoing spin−orbit splitting at
thus, the change of the relativistic influence on the electronic the central atom to the electronegative ligand. For the p-block
structure during the interatomic interactions is accurately elements in high oxidation states with strong ionic bonding
described. partners (such as fluorine) spin−orbit effects become rather
For a very long time it was thought that relativistic effects are small. However, for covalent bonding spin−orbit effects can also
unimportant for chemistry, because the relativistic increase in be substantially reduced by mixing of p1/2 with p3/2 orbitals.
kinetic energy of the electrons in heavy atoms takes place mainly These relativistic orbitals are complex spin α/β mixtures; that is,
at the core electrons close to the nucleus. It was only in the 1970s two p1/2 combinations at different centers give 1/3σ and 2/3π*
when it was discovered that the valence electrons in heavier bonding or a 2/3π and 1/3σ* bonding, while two p3/2
atoms are also affected by relativity and to the extend where the combinations at different centers give one π or a 2/3π and
chemistry of heavy elements is changed significantly.354,368−374 1/3σ* bonding.383 Thus, s-p hybridization and the formation of
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Figure 42. Radial densities D(r) = 4πr2ρ(r) (r in atomic units) for the 1s, 2s, 3s, and 2p states of a hydrogen-like atom with Z = 80. The dashed curves
are nonrelativistic (NR) and the full curves relativistic. The contractions for 1s, 2s, 2p1/2, and 3s are of the same order of magnitude while that for 2p3/2
is much smaller. Reproduced with permission from ref 377. Copyright 1967 Elsevier.
strong σ bonding can be severely hampered if we do not
correctly mix p1/2 with p3/2.383 This is especially the case when
spin−orbit splitting becomes very large, as for the superheavy p-
block elements. For example, the 2P3/2/2P1/2 splitting in the
heaviest rare-gas element known, Og+, is 229 kcal/mol,384 larger
than most bond dissociation energies. Spin−orbit effects have
major influence in systems, which are sensitive to small changes
in energy such as in (first or second-order) Jahn−Teller
distortion385,386 or in dispersive types of interactions.
All the important bonding models for molecules or the solid
state developed in nonrelativistic quantum chemistry can be
transferred and applied to the relativistic domain, even if spin−
orbit coupling is considered. Furthermore, like electron-
correlation effects which can be switched on and off in
calculations, relativistic effects are extremely useful in discussing
anomalies in chemical bonding situations and periodic
trends.387,388
Concerning relativistic effects in the group 1 and 2 elements of
the periodic table,389,390 which are dominated by the direct
relativistic s-shell contraction/stabilization, these are rather
small compared to the corresponding group 11 and 12 atoms
(except for the superheavy elements with nuclear charge 119 and
120).391−393 This was already recognized early on by Pyykkö
and Desclaux.394 In these groups we expect for example small
bond contractions and bond stabilizations for the dimers, which
however will not significantly alter the bonding picture. The
situation completely changes when the electropositive group 1
and 2 elements bind to atoms such as gold, which exhibit very
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strong relativistic effects. For example, in the compound CsAu
the gold atom acts like an electronegative ligand inducing ionic
bonding best described by Cs+Au−,395−397 which is due to the
relativistically increased electronegativity of Au (from 1.9 to
2.4).398 This leads to the interesting situation where solid
Cs+Au− adopts a rocksalt structure rather than being an
intermetallic compound as one would expect399 (two metals
do not necessarily give a metallic bond!). CsAu can be dissolved
in liquid ammonia like several other ionic alkali or alkaline earth
halides,400 and related to this, the interesting coordination
compound AuCs·NH3 has been isolated by Jansen and co-
workers in 2002.401 A similar interesting example is the closed-
shell interaction between Ba and Au− with an unprecedented
high dissociation energy of 34 kcal/mol due to relativistic
effects.402
Far more interesting for relativistic effects in chemical
bonding are the p-block elements. The direct relativistic s-
shell contraction, enhanced by filling the core d-shell, results in
the valence (n)s AOs of the heavy atoms becoming less prone to
chemical bonding; that is, the (n)s electrons retain as lone-pairs
rather than engaging in chemical bonding (inert-pair effect,
originally proposed by Sidgwick403−405). This reduces s−p
mixing in heavy main group compounds and, as a consequence,
destabilizes high oxidation states.406 For example, the non-
relativistic 6s population for TlCl3 was calculated to be 0.73,
while the relativistic one gave 0.96.406 It is well-known that low
valencies in heavy p-block element compounds arise naturally
from the periodic trend down the group in the periodic table
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because of smaller overlap between the more diffuse higher
principal quantum number orbitals; however, relativistic effects
significantly enhance this trend. For example, the TlCl3 → TlCl
+ Cl2 decomposition energy reduces substantially by 42 kcal/
mol (Table 25) due to relativistic effects to a final experimental
Table 25. Relativistic and Nonrelativistic Reaction Energies
(in kcal/mol) of TlX3 (X = F−I) for the Process TlX3(D3h) →
X2 + TlX at the QCI Level Using the Pseudopotential Method
(from Ref 407)
Reaction Nonrelativistic ΔE Relativistic ΔE
TlF3 → F2 + TlF 154.9 105.4
TlCl3 → Cl2 + TlCl 97.0 54.6
TlBr3 → Br2 + TlBr 82.0 45.2
TlI3 → I2 + TlI 63.7 33.5
value of 50 kcal/mol.407 Solid-state effects shift the equilibrium
even more toward the lower oxidation state for thallium; that is,
solid TlCl3 is rather unstable and disproportionates at 40 °C,
loosing chlorine. This originates from the large relativistic
increase of the TlCl dipole moment by more than 1 D,407
leading to stronger ionic interactions in the solid. Concerning
TlI3, it only exists as thallium(I)triiodide in solid form.408
Similarly large relativistic effects are obtained for the halides of
lead.406 For example, Sn(II) and Pb(II) compounds are quite
stable, whereas C(II) and Si(II) require electronic stabilization
in order to be isolated. The influence of relativity on the stability
of group-14 compounds in the oxidation states E(II) and E(IV)
becomes obvious by the calculated reaction energies for the
decomposition ECl4 → Cl2 + ECl2 (E = C − Pb) shown in Table
26. It is clear that there is already a sizable difference between
Table 26. Relativistic and Nonrelativistic Free Reaction
Energies (in kcal/mol) of ECl4 (E = C−Pb) for the Process
ECl4 → Cl2 + ECl2 at the BP86-D3(BJ)/TZ2P Level Using
the Scalar ZORA Approach
Reaction Nonrelativistic ΔG298 Relativistic ΔG298
CCl4 → Cl2 + CCl2 60.9 60.8
SiCl4 → Cl2 + SiCl2 98.0 97.0
GeCl4 → Cl2 + GeCl2 61.4 55.9
SnCl4 → Cl2 + SnCl2 65.2 49.4
PbCl4 → Cl2 + PbCl2 72.4 14.4
nonrelativistic and relativistic values for Ge, which becomes
much larger for Sn and particularly large for Pb. For example,
while CCl4 is a stable compound, PbCl4 decomposes quickly at
50 °C into PbCl2 and Cl2 due to relativistic effects (the gas phase
decomposition energy of PbCl4 has been calculated to be 24
kcal/mol at the CCSD(T) level of theory).409 A nice peculiarity
concerns the lead acid battery, for which we have the overall
reaction Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) +
2H2O(l). The relativistic 6s stabilization destabilizes PbO2, thus
raising the voltage from 0.4 V to the standard value of 2.1 V.410
Thus, lead batteries only work because of relativistic effects.
To illustrate the role of spin−orbit effects, we choose two
prime examples, the dimers Tl2 and Pb2.411−414 Tl2 has an
unusually small dissociation energy of 0.43 ± 0.04 eV.415
Christiansen and Pitzer stated in 1981 that “Tl2 is only weakly
bound... The cause is undoubtedly related to the large spin-orbit
splitting between the 6p1/2 and 6p3/2 thallium spinors”.416 Han and
Hirao calculated that spin−orbit effects increase the bond
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distance by 0.17 Å and reduce the bond energy by about 19 kcal/
mol in Tl2.417 This feature of weak Tl−Tl bonding propagates
into the solid state with Tl having a rather small cohesive energy
of 43 kcal/mol. Further, Tl−Tl interactions in coordination
compounds (termed thallophilic interactions) are rare and
extremely weak, and mostly counterion-mediated, requiring the
anions to provide favorable electrostatics,418 or due to crystal
packing effects.419,420 Similar large spin−orbit coupling effects
are observed for lead. For example for solid lead, nonrelativistic
PW91 results give a cohesive energy of 74 kcal/mol, scalar
relativistic effects reduces it slightly to 70 kcal/mol changing the
crystal structure from diamond to face center cubic, and finally
spin−orbit effects lead to a substantial reduction to reach a final
calculated value of 46 kcal/mol (exp. 47 kcal/mol) and a change
in crystal structure to the hexagonal close packing arrange-
ment.421 Kraka et al. studied the energetics and mechanism for
the hydrogenation reaction XHn + H2 → XHn+1 + H with X
belonging to group 4, 5, 6, or 7 of the periodic table, and found
that spin−orbit coupling becomes very important for the heavier
elements.422,423
The chemistry of short-lived isotopes of superheavy elements
can be studied using atom-at-a-time experiments.424 To prepare
for such experiments, theoretical predictions about their
chemical and physical behavior are required.425 Here, however,
relativistic effects in the bonding of the superheavy elements
become so dominant that they drastically change their chemical
and physical behavior.391−393 The inert-pair effect becomes so
strong for the higher oxidation state that even the fluorides NhF3
and FlF4 decompose easily.426,427 For example, the 7s
population in NhF3 increases dramatically from 0.3 to 1.2 due
to relativistic effects. In fact, NhF3 adopts a T-shape instead of
the expected trigonal-planar structure. Because of strong spin−
orbit splitting in Fl (the 3P0/3P2 splitting is 83 kcal/mol428), Fl
has a closed-shell (7p1/2)2 configuration, and p3/2 mixing into the
Fl−Fl bond to form strong σ- and π- bonding becomes unlikely,
predicting only very weak van der Waals type of interactions.
Indeed, solid-state calculations gave a cohesive energy of only 12
kcal/mol for Fl.421 Pitzer already suggested in 1975 that Fl
should be chemically inert and could even be a gas at room
temperature.429
Moving to the elements where the spin−orbit destabilized
7p3/2 level becomes occupied, B3LYP ZORA calculations by
Mitin and Wüllen show a very large spin−orbit destabilization
for the dimer of tennessine (eka-At), Ts2, from 37 to 11 kcal/
mol due to the inaccessability of the 7p1/2 electrons to form
proper σ-bonds.430 This might be termed as a spin−orbit caused
7p1/2 inert pair ef fect. The rare-gas element oganesson (eka-Rn)
is even more spectacular. The extremely large spin−orbit
splitting results in a rather diffuse and polarizable 7p3/2 shell and
increases the dispersive type of interactions. Hence, Og2 has the
highest dissociation energy of any rare-gas dimer predicted at 1.8
kcal/mol.431 In fact, the electron localization function (ELF)
exhibits a uniform electron gas-like behavior in the valence
region not seen for any of the lighter elements shown in Figure
43.384 The ELF clearly shows the shell structure for the heavier
rare gases Xe and Rn, but for Og the density becomes smeared
out over the whole atom. Moreover, Og has a positive electron
affinity of 1.5 kcal/mol due to the very large relativistic 8s shell
contraction, while all the other rare-gas elements do not bind an
extra electron.432,433 One might therefore speculate that solid
Og has a small band gap and becomes semiconducting or even
metallic due to relativistic effects.434 Further, the diffuse four
7p3/2 electrons can easily be removed to form compounds like
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Figure 43. Electron localization functions from nonrelativistic (NR,
left) and Dirac−Hartree−Fock calculations (R, right) for the heavy rare
gas atoms Xe (top), Rn (middle), and Og (bottom). Reprinted with
permission from ref 384. Copyright 2018 American Physical Society.
OgF4. This structure, however, does not adopt the expected D4h
symmetry but becomes tetrahedral due to strong spin−orbit
coupling.435 This indicates that we expect rather unusual
bonding features in the superheavy element region due to
relativistic effects, which need yet to be explored.
As already mentioned for the Group 1 and 2 elements, strong
relativistic effects in molecular properties also appear when
elements are bound to “relativistic” atoms such as platinum, gold
or mercury. To mention a few examples for the p-block
elements, the strong Pt−C-bond (∼110 kcal/mol) in [Pt-
(CH2)]+ profits from a 50 kcal/mol relativistic stabilization with
the two Pt configurations d8s1 and d9 being involved in the
formation of the Pt−C double bond.436,437 That relativity can
dictate enzymatic reaction was nicely demonstrated by
Kozlowski et al., who showed that mercury methylation by
cobalt corrinoids is dictated by spin−orbit splitting of the Hg 6p
orbitals.438 In this respect, (CH3)2Hg, a highly volatile
compound and a well-known toxin, shows very large relativistic
effects in the Hg−C bond strength.439,440 For many further
examples on relativistic effects including main-group elements,
we refer to a number of review articles.368,370−374,394,441−443
The following conclusions arise from this section:
• Relativistic effects have a strong influence on the
structures and reactivities of heavy main-group atoms.
They become already important for atoms of the fourth
octal row of the periodic system, and they have a
dominant effect on atoms of the fifth and higher rows.
• Relativistic effects make the s-orbitals less inclined to form
chemical bonds. This leads, among other things, to the
stabilization of compounds in low oxidation states and
enhances the inert pair effect for the p-block elements.
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Spin−orbit coupling becomes very important for the fifth
and higher octal rows.
• Quantum chemical methods are now available, which
consider relativistic effects with high accuracy. The
presently most common methods are the ZORA
approximation, Douglas−Kroll−Hess approach, X2C,
and relativistic pseudopotentials. Spin−orbit coupling
can be either included at the Hartree−Fock or Kohn−
Sham level or at a later stage at the correlated level (e.g.,
multireference configuration interaction).
11. CONCLUDING REMARKS
The approach and the relationship of many chemists to the
quantum theoretical explanation of chemical bonding may be
seen as example of Plato’s cave allegory, which is described in his
work Republica.444 It is written as a fictitious dialogue where
Socrates pictures a group of imprisoned people who spent all
their life chained in a cave and facing a blank wall. The people
watch moving shadows projected on the wall in front of them
from a fire behind them. Since these are the only processes
accessible to their senses, the shadows are seen as real objects.
They develop a science of shadows and try to determine laws in
their occurrence and movements and to derive prognoses from
them. They give praise and honor to the one who makes the best
predictions.
One day a prisoner manages to break his chains and he
escapes from the cave. He discovers the sun and realizes that
their reality was not what they thought it was. But the sun “would
hurt his eyes, and he would escape by turning away to the things
which he was able to look at, and these he would believe to be clearer
than what was being shown to him.”444 Slowly his eyes are
adjusting to the light, and the freed prisoner understands that the
real world outside the cave is superior to the world he
experienced in the cave. He is happy about the change, and he
wants to free his fellow cave dwellers out of the cave and into the
sunlight. But returning to the cave would again hurt his eyes,
which have become accustomed to the sunlight, and the
prisoners left behind would infer from the returning man’s pain
that leaving the cave had harmed him and that they should not
undertake a similar journey. Thus, anyone who attempted to
drag them out of the cave would therefore be attacked and
cursed.444−448 The resistance and even hostility of experimental
chemists toward quantum chemistry is a painful experience of
many theoretical chemists.
This work is an attempt to connect the present understanding
of the nature of the chemical bond in terms of quantum theory
with the heuristic bonding models, which were derived from
experimental observations. We do not consider the empirical
models as irrelevant or unimportant shadows on the wall. On the
contrary, they are central ingredients and key variables in
chemical research, which serve as indispensable guidelines for
further development. However, the models must not be
identified with the physical reality of chemical bonding and
interatomic interactions. They should be used on the basis of
and in conjunction with accurate quantum chemical calcu-
lations. The sometimes ambiguous interpretation of exper-
imental results can be better focused in favor of more targeted
planning of further experiments. The laws of physics are only the
framework within which chemical research, with the help of
human creativity and fuzzy concepts, always creates something
new, often with different viewpoints about the interpretation of
chemical bonding. This is not a weakness of chemistry but shows
the limitation of the human mind, which has been expressed by
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Niels Bohr with the saying “We must be clear that when it comes to
atoms, language can be used only as in poetry. The poet, too, is not
nearly so concerned with describing facts as with creating images and
establishing mental connections.”113
AUTHOR INFORMATION
Corresponding Authors
*E-mail: peter.schwerdtfeger@gmail.com.
*E-mail: frenking@chemie.uni-marburg.de.
ORCID
Lili Zhao: 0000-0003-2580-6919
Sudip Pan: 0000-0003-3172-926X
Gernot Frenking: 0000-0003-1689-1197
Notes
The authors declare no competing financial interest.
Biographies
Lili Zhao received her Ph.D. degree at the Graduate University of
Chinese Academy of Sciences in 2012. She then worked in the IHPC,
A*STAR in Singapore as a Scientist during 2012−2014, modeling
homogeneous catalysis. From 2014 to 2016, she held a Humboldt
research fellowship at Philipps-Universität Marburg in Germany. She
joined Nanjing Tech University (China) in the end of 2016 and worked
independently as a full professor. Her research interest include the
homogeneous catalysis, bonding analysis by using state-of-the-art
methods (i.e., EDA, EDA-NOCV, QTAIM), as well as carbone
chemistry.
Sudip Pan obtained his Ph.D. degree from the Indian Institute of
Technology Kharagpur (India) in 2016 under the supervision of Prof.
Pratim K. Chattaraj. In the same year, he moved to work as a
Postdoctoral Fellow at Cinvestav Merida (Mexico) under Prof. Gabriel
Merino. Toward the end of 2017, he moved to Nanjing Tech University
(China) for another postdoctoral stay under Prof. Gernot Frenking and
Prof. Lili Zhao, where he is currently working. His research interests
include the theoretical predictions of viable noble gas compounds,
effective hydrogen storage material, clusters with unusual bonding,
nanomachinery, compounds with boron−boron triple bonds and
reactivity, catalysis and reaction mechanism, planar hypercoordinate
carbon and boron systems, and ligand stabilized species and reactivity.
Nicole Holzmann studied chemistry at the universities Darmstadt,
Bristol/UK, and Marburg. In 2013 she received her doctoral degree in
Theorerical Chemistry at the Philipps-Universität Marburg in the group
of Prof. Dr. Gernot Frenking, where she was working on bonding
analyses of donor−acceptor complexes. From 2014 to 2015 she was a
postdoc with the CNRS (Centre National de la Recherche Scientifique)
at the University of Lorraine with Prof. Chris Chipot and Dr. François
Dehez. During this time she carried out MD simulations of the
membrane proteins. In her current position in the group of Dr. Gilberto
Teobaldi at the STFC (Science and Technology Facilities Council), she
works in close collaboration with user groups and instrument scientists
at the Rutherford Appleton Laboratory facilities and in the area of ab
inito molecular dynamics simulations and TD-DFT.
Peter Schwerdtfeger currently holds a chair in Theoretical Chemistry at
Massey University and serves as Director of the Center of Theoretical
Chemistry and Physics within the Institute for Advanced Study. He
took his first degree in Chemical Engineering (Aalen) and studied both
chemistry and mathematics at Stuttgart University, where he received
his Ph.D. in theoretical chemistry, at habilitated at Marburg University.
He held a position as a software analyst at Stuttgart University before
receiving a Feodor-Lynen fellowship of the Alexander von Humboldt
8835
Review
Foundation to join Auckland University and the Australian National
University. He earned many awards, amongst them the Prince &
Princess of Wales Science Award, the Hector medal, Fellowships of the
Royal Society New Zealand and the International Academy of
Quantum Molecular Science, a James Cook Fellowship and most
recently a Humboldt Research Prize, the Fukui Medal and the
Rutherford medal. His research interests are in fundamental chemistry
and physics.
Gernot Frenking, FRSC, studied chemistry at the universities Aachen,
Kyoto, and TU Berlin where he received his doctoral degree in 1979.
After obtaining his habilitation in theoretical organic chemistry at the
TU Berlin in 1984, he moved to the USA. Following one year as a
visiting scientist with Fritz Schaefer at UC Berkeley he worked at the
Stanford Research Institute in Menlo Park, California. In 1989 he
returned to Germany as Associate Professor for Computational
Chemistry at the Philipps University Marburg, where he was appointed
Full Professor for Theoretical Chemistry 1998 and became Hans-
Hellmann-Professor from 2011−2014. He is also Visiting Research
Professor at the DIPC (Donostia International Physics Center) at San
Sebastian, Spain. Awards include the Elhuyar-Goldschmidt Prize of the
Royal Society of Chemistry of Spain (2007) and the Schrödinger Medal
of the WATOC (2009). In 2019 he received the International Solvay
Chair of Chemistry of the International Solvay Institutes. His research
interests lie in the field of Chemical Bonding Theory and Theoretical
Inorganic Chemistry. Major topics of his work are the nature of the
chemical bond and molecules with unusual electronic structures.
ACKNOWLEDGMENTS
G.F. wants to express his gratitude to Dr. Alfred Paulus for
inspiring suggestions and Prof. Eugen Schwarz as well as Klaus
Ruedenberg for enlightening discussions about the nature of the
chemical bond. He also expresses his gratitude for financial
support by the Alexander von Humboldt foundation and the
Deutsche Forschungsgemeinschaft. L.Z and G.F. acknowledge
financial support from Nanjing Tech University (grant numbers
39837123 and 39837123) and a SICAM Fellowship from
Jiangsu National Synergetic Innovation Center for Advanced
Materials, National Natural Science Foundation of China (grant
no. 21703099), and Natural Science Foundation of Jiangsu
Province for Youth (grant no. BK20170964). S.P. thanks
Nanjing Tech University for a postdoctoral fellowship and the
High Performance Computing Center of Nanjing Tech
University for providing computational resources. P.S. thanks
the Royal Society of New Zealand for financial support in terms
of a Marsden Fund (17-MAU-021) and Prof. Helmut Schwarz
for useful discussions.
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8845 DOI: 10.1021/acs.chemrev.8b00722

Chem. Rev. 2019, 119, 8781−8845