REVIEWS

London dispersion forces in sterically

crowded inorganic and organometallic
molecules
David J. Liptrot and Philip P. Power
Abstract | London dispersion forces are the weakest component of Van der Waals interactions.
They arise from attractions between instantaneously induced dipoles on neighbouring atoms.
Their relative weakness, in particular for light atoms, such as hydrogen, has led to their
importance being largely ignored in discussions of molecular stability and reactivity. This Review
highlights the influence of these attractive forces — usually between C–H moieties in ancillary
ligands — on the physical and chemical properties of organometallic and inorganic molecules.
We feature recent examples of organic species that have informed current thinking and follow
with a discussion of several prominent inorganic and organometallic complexes wherein
dispersion forces have been explicitly identified or calculated. These forces strongly influence the
behaviour of such complexes and often have a defining structural role. Attention is also drawn to
several compounds in which significant attractive dispersion forces are probably present but
have not been investigated.

Terphenyls
In this Review, a terphenyl
ligand consists of a central aryl
ring substituted by two further
aryl rings at the ortho (that is,
flanking) positions relative to
the carbon atom (ipso) through
which the terphenyl ligand is
attached to the reactive centre.
They are denoted by the
abbreviation ArRn, where the
superscript R refers to the type
of substituents on the aryl rings
and the numeral indicates the
number of R substituents
present: for example,
ArMe6 = C6H3-2,6-(C6H2-
2,4,6‑Me3)2 and
Ari-Pr4 = C6H3-2,6-(C6H3-
2,6-iPr6)2.
Department of Chemistry,
University of California,
One Shields Avenue, Davis,
California 95616, USA.
Corresponding to P.P.P
pppower@ucdavis.edu
doi:10.1038/s41570-016-0004
Published online 11 Jan 2017
In his later career, Johannes Diederik van der Waals’
favourite dictum was reportedly ‘all matter displays
attraction’ (REF. 1). Fritz London’s exposition of part of this
attractive force — now known as the London dispersion
force (LDF)2–4 — was fundamental in supporting this
precept. It is therefore remarkable that over the past six
decades, work in synthetic organic, organometallic and
inorganic chemistry has mostly ignored the importance
of these attractive forces. Although workers in protein
science5, as well as those in supramolecular 6 and theo-
retical chemistry, have readily embraced the significance
of dispersion forces, most synthetic molecular chemists
have clung boldly to the simplification that non-bonded
atoms repel each other, as exemplified by steric repulsion.
Nevertheless, work over the past decade has increasingly
revealed the limitations of such a model and, although
organic chemists are becoming aware of the importance of
LDF effects, acceptance in other synthetic sub­disciplines
remains lacking. This Review seeks to remedy this by
highlighting a range of organometallic and inorganic
compounds wherein dispersion forces have been shown
to have a key role in their chemical behaviour.
The use of large, sterically crowded substituents is
fundamental to much synthetic work in both organic
and inorganic chemistry. It is usually assumed that the
main purpose served by the substituents is to hinder the
atom that they are attached to from engaging in reactions
that could lead to decomposition or transformation of
the compounds. This stabilization is caused by the sub-
stituents occupying the space surrounding a reactive
centre7–9 so that access to it is prevented or, alternatively,
by shielding that space through the use of bowl-shaped
or concave ligands. Examples of these ligands are ter-
phenyls10–12 or N‑heterocyclic carbenes13–17 (NHCs; FIG. 1)
bearing aryl substituents, as well as various bidentate
ligands, such as β‑diketiminates, amidinates and
guanidinates, which have similar steric properties18–21.
In virtually all cases, the bulk is provided by one or
more hydrocarbon-substituted groups of various sizes.
The overlap between the electron clouds of these groups
leads to the Pauli repulsive interaction, which may
distort bond lengths and angles. However, in a grow-
ing body of work on hydrocarbon-substituted sterically
crowded molecules, it has been shown that, in addi-
tion to the aforementioned steric repulsion, attractive
dispersion forces (BOX 1) between C–H moieties often
produce results that are difficult to explain purely on
steric grounds22–24. Until recently, it has generally been
assumed that the attractions arising from the LDF are
individually weak and essentially negligible, a misconcep-
tion that is fuelled by the validity of the assumption when
applied to a single pair of light atoms. However, in larger
molecules, LDF effects can be of considerable importance
in collectively inducing stabilization on the order of tens

NATURE REVIEWS | CHEMISTRY VOLUME 1 | ARTICLE NUMBER 0004 | 1

REVIEWS
of kilocalories per mole25. This is sufficient to markedly
influence their physical and chemical properties.
Currently, the importance of LDF effects between
C–H moieties and the resulting stabilization are not
widely recognized, despite attractive interactions between
closed-shell heavy element species (for example, d 10, s 2
and others) having been intensively studied for many
years, and ample structural and spectroscopic evidence
for LDF effects26. Nonetheless, the consequences of the
C–H attractions have recently become apparent through
the experimental and theoretical work of several groups
discussed later (FIG. 2). In addition, the development of
relatively inexpensive quantum chemical methods27
that can estimate LDF effects has provided impor-
tant, often crucial, corroboration, as well as relatively
accurate estimates of their magnitude.
Although non-covalent intermolecular or intra-
molecular forces are not well addressed by density
functional theory (DFT), several approaches28 have been
developed to remedy this problem while preserving
the advantages of DFT. The most common approach
involves a ‘correction’ potential function29–33, such as
that developed by Grimme and co-workers29,30, which is
added to the exchange-correlation functional of choice
and is often denoted by the suffix ‘-D’ after the functional
name. It is also possible to fit the density functionals in
an empirical way so that they include the interactions
attributable to dispersion forces34,35. Furthermore, several
advanced functionals that inherently describe the dis-
persion interactions have been developed36–39 and have
been used for the prediction of, for example, crystal
structures. The dispersion-corrected functionals, which
are subject to continuous review and assessment, are
generally accurate in predictions of structure and
reactivity in many different systems40–49.
This Review focuses primarily on weak, dispersive
interactions between the C–H moieties in substituents,
groups or ligands in organometallic and inorganic com-
plexes. Addressing all cases in which dispersion force
effects may be significant in organometallic compounds
is not our major purpose. Instead, our approach is to
draw attention to several striking examples of organic,
inorganic and organometallic species wherein dispersion
force effects are likely to be of key importance to structure
and reactivity. Obviously, we will only discuss systems in
which dispersion force effects have been explicitly iden-
tified, because there are numerous compounds for which
these effects may be significant but remain unanalysed.
We begin our discussion by presenting some organic
compounds in which the structure and reactivity has
been found to be significantly affected by the LDF.
The following sections are organized around the main
divisions of the periodic table: s block (groups 1 and 2),
p block (groups 13–18), d block (the transition elements)
and f block (lanthanide or actinide). The division of the
compounds into main group, transition metal and lantha-
nide derivatives is mainly one of convenience, but much
similarity can exist in the properties among some classes
of compounds from different blocks of the periodic table.
This Review presents several crystallographically
defined structures, most of which feature interligand
2 | ARTICLE NUMBER 0004 | VOLUME 1
a b c
Si
N Si
E E
E N Si
Inaccessible area
Accessible area
Figure 1 | Examples of large, sterically crowded organic
Nature Reviews | Chemistry
and inorganic substituents. Skeletal structures of a bulky
terphenyl ligand10–12 (part a), a N‑heterocyclic carbene13–17
(part b) and a bulky alkyl ligand (part c). The grey shading
highlights the qualitative effect of a concave structure
(parts a and b) on shielding the area surrounding a reactive
centre, E, or of an alkyl ligand (part c), which occupies a
similar volume. The blue shading qualitatively represents
the coverage of the surface of atom E.
H···H contacts. Such interactions are pictorially repre-
sented when the atoms are within the sum of their van
der Waals radii (2rH = 2.40 Å)50. These crystal structures
feature close arrangements of hydrogen atoms, despite
the repulsive nature of these effects, locally speaking.
Although the stability of molecules with effective steric
repulsion requires additional rationalization, it is possi-
ble that dispersion forces have a contributing role. It is
then reasonable to assume that the large number of such
contacts indicates a strong attraction due to LDFs, hence,
the H···H contacts are highlighted.
Dispersion effects in hydrocarbon molecules
Among recent results on molecular hydrocarbon species,
three can be selected to provide cogent illustrations of
the stabilizing effects of attractive dispersion forces. The
first example concerns the apparent instability of hexa-
phenylethane, which exists as persistent ∙CPh3 radicals
first reported by Gomberg in 1900 (REFS 51,52). On asso-
ciation, these radicals do not dimerize to the expected
C–C bonded substituted ethane Ph3CCPh3, but instead
afford a head‑to‑tail methylenecyclohexadiene unit 53
(FIG. 3a; top structure). By contrast, the more crowded
tert-butyl substituted analogue, the tris(3,5‑di‑tert-
butylphenyl)methyl radical, does lead to the symmetric
ethane derivative (3,5-tBu2H3C6)3C–C(C6H3-3,5-tBu2)3
(REFS 54,55) (FIG. 3a; bottom structure), which is a stable,
colourless, crystalline solid (melting point = 214 °C) and
has a lengthened C–C bond of 1.67(3) Å (REF. 55).
A computational analysis of the structure by Grimme
and Schreiner 24 confirmed the greater steric crowding,
but also indicated that the meta tert-butyl groups on the
aryl rings did not add significantly to the Pauli repul-
sion already present in hexaphenylethane because of
their location at the meta positions of the phenyl rings.
However, the computations incorporating dispersion
www.nature.com/natrevchem

energy disclosed a very large, about 70 kcal mol−1, stabi-
lization energy arising from attractive LDF between the
C(C6H3-3,5-tBu2)3 fragments. This energy is more than
sufficient to make the structure stable against dissoci-
ation (bond dissociation energy (De) = 35.2 kcal mol−1).
The calculations reproduced the structural parameters
accurately, including the key central C–C bond length
of 1.661 Å, in agreement with the experimental value of
1.67(3) Å. By contrast, calculations without a dispersion
correction predict instability with a negative value for De
of −26.4 kcal mol−1 — a difference of over 60 kcal mol−1
from the De of +35.2 kcal mol−1 given above.
A further powerful example illustrating the effect of
the LDF can be found in the work of Fokin, Schreiner
and co-workers on ethane derivatives bearing highly
rigid diamondoid substituents such as those based on
adamantyl (–C10H15)22,23,25,56,57. Among these is a molecule
— stable up to 300 °C — featuring a central C–C bond of
1.647 Å between two diamantane units. Another example
is 2-(1‑diamantyl)[121]tetramantane, which has a central
C–C bond, here between diamantane and triamantane
units, that is even longer (1.71 Å; FIG. 3b)23. The structures
of these and related species are well-reproduced by DFT
calculations using dispersion-corrected hybrid func-
tionals31–35. The high thermal stability of the structures
results from numerous attractive interactions between
neighbouring hydrogen‑terminated diamond-like
surfaces25,56,57, and such forces also greatly increase the
barrier to rotation around the central C–C bond from
about 7 to 33 kcal mol−1.
The third example is tetra(tert-butyl)tetrahedrane
(CtBu)4 (REFS 58–60), a molecule with a high strain
energy of 129–137 kcal mol−1. The stability of this species
was originally interpreted on the basis of the interac-
tion between tert-butyl substituents. It was argued that
the decomposition of the molecule by stretching a tet-
rahedrane C–C bond, promoted by repulsion between
tert-butyl groups, is counterbalanced by the attractive
interactions between the stretched unit and the remain-
ing tert-butyl groups — a so‑called corset effect. More
Box 1 | Origin of London dispersion force
The London dispersion force (LDF)2–4 arises from the attraction of instantaneous
molecular multipoles originating from electron correlation. It is one of the three major
attractive components of the van der Waals forces between molecules, the remaining
two being: the force between two permanent dipoles (Keesom force) and the force
between a permanent dipole and a corresponding induced dipole. The stabilization
energy produced by the attractive LDF between two atoms, A and B, can be
approximated on the basis of their polarizability volumes (α), first ionization potentials
(I) and their separation (R).
3 IAIB αAαB
disp
EAB ≈−
2 IA + IB R6
The LDF is highly dependent on distance, evident from the R−6 factor in this
approximation. It is considered the weakest of intermolecular forces, typically being
≤1 kcal mol−1 for interactions between atoms (and lower for hydrogen atoms). However,
this increases with atomic number, molecular size, contact area and polarizability. The
LDF is present intramolecularly and its collective effect can be substantial (tens of
kcal mol−1) in large molecules. Thus, the LDFs can be significant enough to considerably
influence physical and chemical properties of large molecules.
NATURE REVIEWS | CHEMISTRY
REVIEWS
recent calculations have indicated that the parent tetra-
hedrane should also be kinetically stable61. Nonetheless,
the synthesis of (CtBu)4 was deemed astonishing at
the time, because the tert-butyl substituents lower the
thermo­stabilization of the C–C bond, and it was noted
that the valence-bond isomerization to cyclobutadiene
or fragmentation to two molecules of the corresponding
acetylene is orbitally forbidden. The proposal that LDF
effects stabilize (CtBu)4 is therefore an appealing one;
calculations on this species support this view 22.
Main group species
Importance of LDF effects in molecules with single
bonds between main group elements. Realization of
the importance of LDF effects on single bond lengths
originated from studies of main group compounds
with very bulky ligands, particularly those featuring
supersilyl (–SitBu3) and related groups62. Experimental
studies on the synthesis, structure and properties of
cyclo-tert-butyltrisilane63 c-(SitBu2)3 and hexa-tert-
butyldisilane64 tBu3SiSitBu3 (FIG. 4a) in the 1980s have
shown that these compounds have extremely long
Si–Si and Si–C bonds: for example, 2.511(3) Å and
1.99 Å in c-(SitBu2)3 and 2.697 Å and 1.970(5) Å in the
disilane (predicted Si–Si and Si–C single bond lengths
for the disilane are 2.34 and 1.88 Å, respectively)65. In
the cyclotrisilane, the highlighted distances correspond
to Pauling bond orders66,67 of 0.60 and 0.75, respectively.
It was estimated that the Si–Si distance was equivalent
to a C–C distance of 1.70 Å (REF. 61) (similar to the C–C
distance of 1.71 Å in 2-(1‑diamantyl)[121]tetramantane
noted earlier; FIG. 3b)23. By contrast, the Si–Si distance in
the disilane corresponds to a lower Pauling bond order
of 0.45 (REF. 63). Despite the long element–element bonds
that suggest instability, both compounds displayed sur-
prisingly high thermal robustness, were stable towards
air and moisture, and had relatively high melting points
of 182 °C for c-(SitBu2)3 and 162 °C for tBu3SiSitBu3. In
the early 1990s, Bock and co-workers68 reported the
related disilane (Me3Si)3SiSi(SiMe3)3, which had a cen-
tral Si–Si bond length of 2.405(5) Å. However, they noted
close contacts between the peripheral SiMe3 groups and
suggested these to be responsible for the surprising
stability of this molecule.
Further work on the related germanium and tin
analogues supported this view 69,70. The structures of
c-(GetBu2)3 and tBu3GeGetBu3 (REF. 69) feature the longest
known Ge–Ge and Ge–C single bonds: 2.563(1) and
2.056(3) Å for c-(GetBu2)3 and corresponding values
of 2.710 and 2.076 Å in tBu3GeGetBu3. In addition, the
Ge–Ge and Si–Si distances in the tBu3EEtBu3 (E = Si or
Ge) species — 2.697 and 2.705(1) Å, respectively — were
almost equal, despite the different radii of these ele-
ments (Si = 1.17 Å, Ge = 1.22 Å)65. These findings further
emphasize the importance of LDF stabilization as being
distinct from stabilization attributable to covalent bond-
ing between the E sites of the –EtBu3 moieties. As with the
silicon analogues, the germanium compounds are hydro-
lytically and thermally stable. On the other hand, the
distannane tBu3SnSntBu3 (REF. 70) features a Sn–Sn bond
(2.894(1) Å) that is only moderately elongated relative to
VOLUME 1 | ARTICLE NUMBER 0004 | 3
REVIEWS

a normal Sn–Sn single bond (2.80 Å)65. This is probably
due to tin being much larger than germanium and silicon,
which relieves steric repulsion in the present case.
The study of other compounds incorporating
–SitBu3 substituents provides further evidence of the
importance of LDF effects62,71. The reaction of NaSitBu3
with Sn[N(SiMe3)2]2 or Sn(OtBu)2 at −25 °C affords
the tristannaallene Sn[Sn(SitBu3)2]2. On warming, this
species isomerizes to cyclotristannene c-Sn3(SitBu3)4,
which can also be prepared by carrying out the reaction
at room temperature71. The Sn3 ring structure is nota-
ble since its Sn–Sn double bond is 2.59(1) Å in length,
which is the shortest known Sn–Sn distance in a sta-
ble compound, including the nominally triple-bonded
distannynes (about 2.64–2.67 Å)72.
It was noted that in the ring structure of c-Sn3(SitBu3)4,
the four –SitBu3 groups roughly occupy the edges of a
tetrahedron, thus adopting a close packing arrangement,
presumably LDF-assisted, which obscures the Sn3 ring
almost completely 71.
Another example of the stabilizing effects arising
from the –SitBu3 ligand can be found in derivatives of
the neighbouring group 13 metals. The reaction of three
equivalents of NaSitBu3 with AlX3 (X = Cl or Br) affords
the dialane(4) tetrasilyl derivative (tBu3Si)2AlAl(SitBu3)2
(REF. 73) (FIG. 4b). The compound features two planar coor-
dinated aluminium atoms with coordination planes that
are staggered with respect to each other. The Al–Al bond
length is 2.751(2) Å, which is unusually long and about
0.1 Å longer than those in other tetraorgano dialanes
(R2AlAlR2, where R is CH(SiMe3)2 (REF. 74) or C6H2-
2,4,6-iPr3 (REF. 75)). In solution it exists in equilibrium
with a very low concentration of the radical Al(SitBu3)2,
and its treatment with H2 or I2 yields (tBu3Si)2AlX (X = H
or I). The monomer–dimer equilibrium is strongly
tilted towards the dimeric form, because the Al(SitBu3)2
‘halves’ are bonded not only by a weak Al–Al covalent
interaction, but also by LDFs between the peripheral CH3
substituents73. Tetra-tBu3Si-dimetallane derivatives of
indium and thallium also feature moderately length-
ened M–M (M = In or Tl) distances 76. The gallium
derivative has a more complex chemistry owing to the
increased steric crowding caused by the smaller size
of this element 65. This does not permit formation of
(tBu3Si)2GaGa(SitBu3)2, but instead affords the radical
species (tBu3Si)GaGa(SitBu3)2 (REF. 77).
LDF effects on compounds with multiple bonds. The
study of compounds with multiple bonds between main
group elements, particularly between the heavier group
members, continues to be a highly dynamic research area
that constitutes a major portion of current investigative
work on main group molecular species78,79. It is now
widely accepted that the majority of such bonds differ
fundamentally from those of their lighter congeners,
as indicated, for example, by non-planar or non-linear
coordination in the heavier element analogues of ethyl-
ene and acetylene. In the past, the multiple bonding in
such compounds was often characterized by argument
and controversy, mainly centred on the concept of bond
order 78. The eventual outcome of this debate was that
Pythagorean bond orders (that is, those that can be
written as whole numbers or as fractions thereof) prev-
alent in organic chemistry have limited applicability in
heavier-element species. Ironically, more recent findings
have shown that the orbital overlap between the heavier
elements in many of the multiply bonded species can be
of lower strength than the attractions arising from the
LDF between the ligands, thereby reducing the impor-
tance of the arguments regarding bond orders. As it is
now described, the recent literature has provided several
examples of compounds that illustrate this point.

Theory Computational Suggestion that the stability

Inorganic and organometallic Organic
M[N(SiMe3)2]3 (M = Sc, Eu)
Van der Waals’ thesis structurally characterized;
defines intermolecular pyramidalization
interactions (German attributed to attractive
translation, 1877; English intramolecular
translation, 1890)1 dispersion interactions116
of (Me3Si)3SiSi(SiMe3)3 is Donor–acceptor singly bonded diplumbylene
related to the close contact synthesized and shown to be principally
between SiMe3 substituents68 stabilized by dispersion attractions80
Development of DFT-D methods Increased dispersive interactions
allowing the accessible assessment and between the ligands gives
reassessment of dispersion force effects access to M[N(SiMe3)Dipp]2
in molecular structures27,29,30,32–34,37,42 (M = Fe–Cu)131,133

1873 1930 1973 1986 1993 1995 1998 2004 2011 2012 2013 2016

London dispersion M(Cp*)2 (M = Sc, Eu)
forces are found to structurally characterized;
contribute to van der bent structure observed
Waals interactions2 and calculated to be due
to attractive
intramolecular dispersion
interactions97,98
(tBu3Si)2AlAl(SitBu3)2
synthesized, its stability,
despite weak Al–Al
bonding, is attributed
to dispersion62
Hexaphenylethane Molecules with Heavier main group
riddle solved using long C–C multiple bonding
newly developed DFT-D bonds reassessed in light of
methods indicating the stabilized by attractive London
importance of dispersion are dispersion using
intramolecular designed and DFT-D methods80,82,84,86
dispersion interactions24 synthesized22,23

Figure 2 | Timeline of the relevant advances in the study of London dispersion forces in organic and inorganic
compounds. A timeline highlighting the milestones in theory and experiment that led to the current understanding of
Nature
the role of London dispersion forces in the structure and reactivity of sterically crowded inorganic andReviews | Chemistry
organometallic
molecules. Cp*, C5(CH3)5; Dipp, 2,6‑diisopropylphenyl; DFT-D, dispersion corrected (-D) density functional theory.

4 | ARTICLE NUMBER 0004 | VOLUME 1 www.nature.com/natrevchem

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a R
b (E = Ge, Sn or Pb; FIG. 5b) and their dissociation into
R
R E[CH(SiMe3)2]2 and E[N(SiMe3)2]2 monomers were
R
R=H H
H performed. When the alkyl derivatives are considered
H
R H
C C
R R H
R R
H H
R
R R
R R R
R R
R C–C = 1.71 Å
R LDF stabilization energies falling in the range of about
R R
c 15.2–28.7 kcal mol−1 for the three classes of compounds.
R t
C C Bu
R In addition, thermodynamic calculations indicated that
R = tBu
R
R
R R
t
Bu t
Bu
t
Bu
R Clearly, the LDF effects are of greater importance
C–C = 1.67 Å C–C = 1.495 Å (calculated)
Figure 3 | London dispersion force effects in organic molecules. a | Contrasting
Nature Reviews | Chemistry
association of the ∙CPh3 and ∙C(C6H3-3,5-tBu2)3 radicals. Unsubstituted ∙CPh3 leads to a
quinoid-type methylenecyclohexadienyl structure (top)53, whereas the tert-butyl
substituted derivative leads to a C–C bonded ethane structure (bottom) with a long C–C
bond of 1.67 Å (REF. 55). b | A diamondoid ethane derivative with bonding between
triamantane and diamantane moieties that has a C–C bond length of 1.71 Å (REF. 23).
c | A substituted tetrahedrane with calculated central C–C bond lengths of 1.495 Å
(REF. 59) or 1.484 Å (REF. 60). All of these structures have been shown to be stabilized by
London dispersive attractions22–25.
The dimerization of a cyclic disilylated plumbylene
(a lead analogue of a carbene) is a reaction that occurs,
according to calculations by Marschner, Müller and
co-workers80, as a result of attractions arising from
the LDF (FIG. 5a). A plumbylene phosphine complex is
formed by the reaction of 1,4‑dipotassio‑1,1,4,4‑tetra­
kis(trimethylsilyl)-2,2,3,3‑tetra­methyltetrasilane with
PbBr2 in the presence of PEt3. Treatment of the complex
with B(C6F5)3 removes PEt3 as Et3PB(C6F5)3 and causes
the plumbylene monomer to dimerize, with the lead
atoms being linked through an unusual single donor–
acceptor bond (3.0640(8) Å), resembling that observed
in the distannene [Sn(C6H-2‑tBu‑4,5,6‑Me3)2]2 (REF. 81).
This type of association is much rarer than the double
donor–acceptor element–element bond, which is more
commonly observed in heavier group 14 dimetallene
dimers78,79. The binding energy of the plumbylenes in
the dimer was computed to be 26.4 kcal mol−1, which
is 11.5 kcal mol −1 stronger than that in the parent
diplumbene (that is, H2PbPbH2). The predicted structure
was in good qualitative agreement with the experimental
data, but the charge transfer between the plumbylene
units was calculated to contribute only about 25% to
the bond energy. In effect, most of the binding energy
between isolated plumbylenes is LDF-based. The unu-
sual results are consistent with the absence of a correla-
tion between the out‑of‑plane torsion angle and bond
Extended transition state– length in the heavier ditetrelenes, in which much of the
natural orbitals for chemical attraction between the two tetrylene ‘halves’ is due to
valence LDF effects, rather than tetrel (that is, group 14) element
(ETS–NOCV). A scheme for the orbital overlap78,79.
analysis of chemical bonds
based on the decomposition of
More recently, dispersion-corrected DFT calcula-
the bonding on the basis of tions82 on the group 14 ethylene analogues [(Me3Si)2HC]2­
charge and energy90. EE[CH(SiMe 3) 2] 2 and [(Me 3Si) 2N] 2EE­[ N(SiMe 3) 2] 2
without including a dispersion force correction, asso-
ciation is only favoured by about 2.1 kcal mol−1 for the
tin species, whereas dissociation is favoured for the
germanium and lead derivatives. However, inclusion
of LDF correction by the Grimme method shows that
association becomes much more strongly preferred, with
dimerization of germanium and tin fragments (but not
lead) is energetically favoured overall.
than covalent E–E bonding in the association ener-
gies of these monomers. Calculations for the amido-
substituted analogues [(Me 3Si) 2N] 2EE[N(SiMe 3) 2] 2
reveal LDF-based attraction between the C–H
groups of the –N(SiMe 3) 2 ligands, although mon-
omeric structures are still observed partly because
of the E–E bonding being weakened by the pres-
ence of more electronegative –N(SiMe3)2 substitu-
ents. In addition, the distannene (tBu 2MeSi) 2SnSn
(SiMetBu2)2 (REF. 83) has been shown to have a unique
structure with a very short Sn–Sn bond of 2.647 Å.
Although it has planar coordination at each tin centre,
which would normally suggest strong multiple-bonding
character for the Sn–Sn bond, the coordination planes
at each tin are twisted by 44° with respect to each other.
This is contrary to the traditional σ–π double bond model
having a 0° torsion angle and indicative of a weakened
interaction. Calculations 84 instead show that LDF effects
are key to the stability of the compound, stabilizing the
molecule by 21 kcal mol−1 (REFS 82).
Parallel calculations on the sterically related group
15 [(Me3Si)2HC]2EʹEʹ[CH(SiMe3)2]2 and [(Me3Si)2N]2­
EʹEʹ[N(SiMe3)2]2 (Eʹ = P or As)84 dimers showed that
without the inclusion of LDF effects, cleavage of the
Eʹ–Eʹ bond to form the monomeric radicals is favoured.
Inclusion of LDF effects shows that the dimeric
diphosphane or diarsane structures become favoured.
Moreover, it was shown that the attractions arising from
LDFs are more than sufficient to overcome the so‑called
Jack‑in‑the-box conformational change85 from syn, anti
to syn, syn (FIG. 5b), a process that otherwise leads to
dissociation when the dimers are dissolved or vaporized.
Despite the importance of LDF effects, a common
feature of all the dimeric species discussed before is that
the E–E interactions, although weak, are always pres-
ent, and their role in directing dimer formation in the
first place cannot be discounted. Other computational
studies of triply bonded main group compounds86 have
also uncovered LDF effects, one example being from
the work of Ziegler and co-workers, which involved the
bonding in heavier main group element alkyne ana-
logues ArEEAr (where Ar is a terphenyl ligand (FIG. 1a)
and E = Si, Ge (REF. 87), Sn (REF. 88) or Pb (REF. 89)). For the
silicon, germanium and tin species, an extended transi-
tion state–natural orbitals for chemical valence (ETS-NOCV)90
analysis based on doublet EAr fragments revealed that

NATURE REVIEWS | CHEMISTRY VOLUME 1 | ARTICLE NUMBER 0004 | 5

REVIEWS
a σ bond, a π bond perpendicular to the –CEEC– plane
and a slipped π bond in the molecular plane constitute
the triple bond. In contrast, ArPbPbAr was found to
have a single Pb–Pb σ bond only with an ipso‑C–Pb–Pb
angle close to 90°. The stabilizing influence of the iPr
groups arises from attractive LDFs between the C–H
moieties, along with hyperconjugative donation into the
σ* orbitals of the iPr groups. The dispersive interactions
were calculated to be 27.5 kcal mol−1 (Si), 29.1 kcal mol−1
(Ge), 26.2 kcal mol−1 (Sn) and 44 kcal mol−1 (Pb). The
larger value for lead is connected to the terphenyl sub-
stituent used for that metal, which has a greater number
of iPr substituents (six versus four) on each terphe-
nyl ligand. The relatively high values of the calculated
dispersion energies (≥26.2 kcal mol−1) reflect the stabiliza-
tion influence of these effects in the present compounds.
Similarly, the optimized crystal structure of Jones’ dimer
a
b ences in energy between the bent and linear forms are
Carbon Hydrogen Short contacts,
probable London
Silicon Aluminium
dispersion interaction
Figure 4 | London dispersion Nature
force effects in superilyl
Reviews | Chemistry
and related groups. a | Crystal structure of tBu3SiSitBu3
with a long Si–Si bond length of 2.697 Å (REF. 64). b | X-ray
crystal structure of (tBu3Si)2AlAl(SitBu3)2 with a long Al–Al
bond length of 2.751(8) Å (REF. 73). Both structures show
selected hydrogen atoms where interligand distances are
shorter than the sum of the van der Waals hydrogen radii
(≤2.4 Å)50.
6 | ARTICLE NUMBER 0004 | VOLUME 1
LMg(i)–Mg(i)L (L = HC[CMe{N(C6H2-2,6-iPr2)2}2])
highlights that it is held together mainly through
LDF effects91.
More recently, the stabilization resulting from attrac-
tive LDF effects has been evaluated for a series of mul-
tiply bonded B–B, Si–Si and P–P species, and related
compounds featuring bulky N‑heterocyclic carbene lig-
ands92. Dispersion corrections upwards of 30 kcal mol−1
were calculated and it was concluded that LDF effects
contribute critically to the thermodynamic stabilities of
these compounds. The reactivity of these species towards
small molecules and their redox chemistry has been
experimentally assessed92. Computational interrogation
of these results indicated that chemical transformations
at the central E–E moiety occurred with conservation
of the dispersive shell: that is, with limited rearrange-
ment of the ligands owing to their highly dispersive
nature. Dispersion force effects have also been implicated
in complexes of the related N‑heterocyclic silylene, which
yields a three‑coordinate silylene adduct of Fe[N(SiMe3)2]2
wherein the dispersion attraction was calculated to be
22.7 kcal mol−1 (REF. 93). Dispersion force effects have
also been implicated in driving the Wagner–Meerwein
rearrangement of oligosilane cations94.
Among the earliest papers proposing C–H···H–C
LDF-based interactions as a possible explanation for
the unusual structures of organometallic molecules in
both main group species and lanthanides were those
that reported the structures of η5-C5Me5 (Cp*) deriva-
tives, M(Cp*)2 (M = Mg, Ca, Yb, Sr or Ba)95–98. For such
compounds it was proposed96–99 and calculated100,101 that
LDF effects involving the Cp* rings cause the molecu-
lar geometries to be bent. The calculated and observed
structures corresponded closely. However, the differ-
relatively small.
The probable influence of attractive dispersion forces
on molecular structure is also seen in the divalent chal-
cogenolato substituted tetrylenes (carbene analogues). A
series of heavier element carbene analogues of formula
E(SArMe6)2 (E = Si, Ge or Sn; ArMe6 = C6H3-2,6(C6H2-
2,4,6‑Me3)2), E(SAri-Pr 4)2 (Ari-Pr 4 = C6H3-2,6(C6H3-2,6-
i
Pr2)2), E(SAri-Pr 6)2 (Ari-Pr 6 = C6H3-2,6(C6H2-2,4,6-iPr3)2)
and E(SAr i-Pr 8) 2 (Ar i-Pr 8 = C 6H-2,6(C6H 2-2,4,6-iPr 3) 2-
3,5‑Pr2), in which the bulk of the terphenyl thiolato
substituent is enhanced by increasing the number and
size of the alkyl groups attached to the terphenyl substi-
tuted ring 102. However, contrary to steric expectations,
the increase in substituent size leads to a decrease, rather
than an increase, in the S–E–S angle at the central tet-
rel to below 90° (TABLE 1). In addition, it was also found
that as the bending angle decreased, the torsion angle
between the central aryl rings of the terphenyl substitu-
ents also decreased. Experimental and structural data in
conjunction with high-level DFT calculations, including
corrections for dispersion effects, led to the conclusion
that LDFs between the alkyl substituents stabilized the
observed acute interligand angles102.
Another bulky ligand remarkable for the stabiliza-
tion of many unusual compounds is the well-known
tris(trimethylsilyl)methyl group –C(SiMe 3) 3. Some
www.nature.com/natrevchem
 REVIEWS

examples of complexes bearing this ligand are now persistence of the anionic motif can also be seen in the
described, including the seminal work of Eaborn, copper(i) complex of tris(trimethylsilyl)methanide
Smith and co-workers103. The metals of the s block (FIG. 5c), a rare structurally characterized two‑coordi-
provide an ideal proving ground for dispersion force nate dialkylcuprate. This compound is isostructural to
effects, because the non-directional bonding of these the lithium salt, also suggesting the effects of LDF on
elements allows such small forces to have significant this structure109.
structural effects. In contrast to the usual associated Group 2 bis[tris(trimethylsilyl)methanide] com-
structures, the lithium and sodium derivatives of this pounds also exhibit noteworthy structural parameters,
ligand both exhibit an unusual charge-separated struc- the two extreme cases being the magnesium and cal-
ture of the form [M{C(SiMe3)3}2]− (M = Li or Na)104–106. cium derivatives. Mg[C(SiMe3)3]2 is linear and surpris-
Inspection of these congeners indicates that the elon- ingly inert for a dialkylmagnesium compound110,111, as
gated M–C bonds in the sodium derivative result in opposed to the calcium derivative that features a more
the rotation of trimethylsilyl substituents to maxim- notable bent C–Ca–C angle of 149.7(6)° (REF. 112). The
ise H···H contacts, suggesting a structural effect of presence of short interligand H···H contacts in the crystal
interligand dispersion interactions. Furthermore, structure of the latter suggests that the forces resulting
although this isomeric form persists for the slightly in this bent structure may be similar to that for Ca(Cp*)2
modified –C(SiMe3)2(SiMe2Ph) ligand for lithium107, (REF. 100) — that is, attractive LDFs.
the structural constraints imposed on the methyl sub- Similarly, attractive dispersion forces between ligands
stituents in –C(SiMe2Ph)3 perturbs the potential of are likely to contribute to the surprising stability of
the interligand dispersion forces to yield the solvated group 12 complexes incorporating two very bulky alkyl
lithium alkyl [Li{C(SiMe2Ph)3}(THF)] (REF. 108) rather ligands. Thus, Zn[C(SiMe3)3]2 (REF. 113) shows anoma-
than the dissociated ionic structure observed for the lously high stability for a dialkylzinc and can be steam
–C(SiMe3)3 or –C(SiMe3)2(SiMe2Ph) derivatives. The distilled under air. This is in contrast to the usual flam-
mability of this class of compounds in the presence of
oxygen. Dibenzylmercury was found to be around 4,500
a RR
b times more susceptible to unimolecular dissociation
Si
Si syn, syn syn, anti than Hg[C(SiMe2Ph)3](CH2Ph), behaviour that was
R
Si
Pb Pb R R R attributed to the transfer of energy from vibrations of
Si R Si Si R H R
H R the large ligand to bond dissociation114. In both of these
R Si Si R H
R R E E E cases, interligand attraction was not considered but is
H R
H R
R = SiMe3 R R likely to be a contributing factor to these anomalously
R R H
high stabilities115.
R = SiMe3 E = Ge, Sn, Pb
c R R Transition and lanthanide metal complexes
R
M It is probable that the first publication to attribute
R R
R structural distortion to London dispersion effects in
R = SiMe3 M = Li, Na, Cu
an inorganic molecular species concerned the three-
coordinate transition metal and lanthanide amido
derivatives M[N(SiMe 3) 2] 3 (M = Sc and Eu), which
displayed a pyramidalized rather than planar metal
coordination116. It was suggested that distortion from
planarity occurs on formation of the crystalline phase,
in which the metal ion is squeezed out of the coordina-
tion plane by a symmetrical contraction resulting from
intra­molecular–interligand van der Waals attractions.
However, dipole moment measurements suggest that
the pyramidal structure is not preserved in solution.
Another early possibility is the ytterbium species
Yb(Cp*)2 (REF. 94), which has a close structural resem-
Carbon Hydrogen Silicon Short contacts, probable blance to the group 2 bis(pentamethylcyclopentadienyl)
London dispersion interaction
Tin Lithium metal M(Cp*)2 (M = Mg, Ca, Sr or Ba)95–99 species. These
have bent structures (also in the vapor phase)95–97, as do
Figure 5 | London dispersion force effects on molecules with multiple bonds the divalent lanthanide derivatives Mʹ(Cp*)2 (Mʹ = Sm or
Nature Reviews bond
between main group elements. a | Unusual side‑on single donor–acceptor | Chemistry
in Eu)117–119. In the samarium species, the shortest distance
diplumbylene stabilized by London dispersion forces80. b | Association of group 14
between the methyl group carbons is 3.34(1) Å, which is
element monomers gives dimers with rotated substituents82 and the X-ray crystal
less than the sum of their van der Waals radii (3.4 Å)50.
structure82 of [(Me3Si)2HC]2SnSn[CH(SiMe3)2]2. c | The unusual structure of anionic
group 1 and group 11 metal complexes of the tris(trimethylsilyl)methane ligand104–109 The very crowded complex Sm(Cp*)3 (obtained from
and the X-ray crystal structure104 of the dialkyllithium [Li{C(SiMe3)3}2]− anion. The Sm(Cp*)2 by a disproportionation reaction with cyclo­
[Li(THF)4]+ counterion is not shown for clarity. Crystal structures in b and c show selected octatetrene) shows significant structural strain and a
hydrogen atoms where interligand distances are shorter than the sum of the van der fascinating chemistry in light of its probable stabilization
Waals hydrogen radii (≤2.4 Å)50. by LDFs between ligands120.

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REVIEWS

More recently, there has been a rapid increase in the
number of publications on LDF effects on the stability,
structure and reactivity of various transition metal
complexes. Compounds studied include Pd(PPh3)4
(REF. 121), Pd(PtBu3)2 (REF. 122), and group 8 species such
as Os(Cl)2(H2)(PiPr3)2 (REF. 123). Computational studies
were performed on ruthenium olefin metathesis cata-
lysts of formula Ru(Cl)2(PR3)2(NHC) (REF. 124), in which
various basis sets and their effects on phosphine dissoci-
ation barriers were also evaluated125. Furthermore, steric
attraction has also been shown to have decisive influence
on bite angle in two‑coordinate transition metals and
a consequent effect on reactivity 126. In addition, H···H
interactions in some metal hydride complexes were also
shown to arise from dispersion forces127.
In comparison to the sterically crowded main group
species discussed earlier, LDF effects are less studied in
sterically crowded transition metal complexes with alkyl,
aryl or amido ligands. However, a few calculations have
indicated that dispersive interactions are of great impor-
tance for the stabilization of transition metal complexes
bearing such ligands86,128. In parallel with the heavier
group 14 element alkyne analogues Ar i-Pr 4EEAr i-Pr 4
(E = Ge or Sn) and Ari-Pr 6PbPbAri-Pr 6 mentioned above,
calculations 128 on the quintuply bonded species
Ari-Pr 4CrCrAri-Pr 4 bearing the same ligand as the ger-
manium and tin species129 (FIG. 6a) have confirmed five
distinct bonding components to the Cr–Cr bond, as well
as the presence of secondary Cr–C interactions involv-
ing the ipso carbon of the terphenyl group. However, the
presence of the isopropyl substituents stabilizes the mol-
ecule by 20 kcal mol−1 relative to the CrAri-Pr4 monomers,
as a result of LDF effects between these groups.
A characteristic of transition metals is their tendency
to display a range of oxidation states that differ by unity
steps. This stems from the presence of several energeti-
cally accessible d orbitals. The modest energies that often
separate the stabilities of complexes in various oxidation
states make them more susceptible to disproportionation.
The use of –N(SiMe3)Dipp (Dipp = C6H3-2,6-iPr2)
ligand has recently permitted preparation of the first
two-coordinate130 Cu(ii) complex, Cu[N(SiMe3)Dipp]2
(REF. 131) (FIG. 6b). Its formation apparently takes place by
a dispersion energy-influenced disproportionation of a
Cu(i) complex formed by the reaction of LiN(SiMe3)Dipp
with CuCl in non-donor solvents. Also, it is possible that
in the synthesis of the homoleptic vanadium(ii) amide
V[N(H)Ari-Pr6]2 from a vanadium(iii) starting material132,
reduction to the vanadium(ii) product occurs through
a disproportionation (analogous to the formation of
Cu[N(SiMe3)Dipp]2 (REF. 131); FIG. 6b) with concomi-
tant formation of an unidentified vanadium(iv) spe-
cies. Dispersion force effects in heteroatom-substituted
terphenyls have precedent 102, suggesting that this puta-
tive disproportionation is partly assisted by attractive
dispersion forces between the bulky ligands.
Stabilizing London dispersion interactions were
also calculated for two-coordinate amido complexes of
formula M(ii)[N(SiMe3)Dipp]2 (M = Fe, Co or Ni)133,
as well as the Ni(i) tetramer [Ni{N(SiMe3)2}]4 (REF. 134).

Table 1 | Correlation between ligand size and structural properties in dithiolatotetrylenes

Ligand E(SAr)2 E–S bond length S–E–S bond Torsion angle (°)
(Å) angle (°) between ES2 and
central aryl ring plane
Si(SArMe6)2 2.158(3) 90.52(2) 44.9(1)
S
Ge(SArMe6)2 2.265(11) 88.68(2) 40(6)

Sn(SArMe6)2 2.479(5) 85.555(3) 38(10)

Si(SAri-Pr4)2 2.137(1) 85.08(5) 38.2(2)

iPr iPr
S
Ge(SAri-Pr4)2 2.284(4) 81.26(2) 32.3(1)
iPr iPr
Sn(SAri-Pr4)2 2.470(1) 78.63(3) 31.2(3)

iPr iPr iPr iPr

Si(SAri-Pr6)2 2.089(9) 84.8(1) 29(7)
S
Ge(SAri-Pr6)2 2.24(4) 79.6(2) 27(7)
iPr iPr
Sn(SAri-Pr6)2 2.46(6) 78.2(2) 34(6)

iPr iPr iPr iPr

Ge(SAri-Pr8)2 2.2940(6) 77.01(2) 3.6(2)
S
Sn(SAri-Pr8)2 2.5009(6) 73.09(2) 3.8(2)
iPr iPr
iPr iPr

This table shows the effects of increasing steric bulk of the terphenyl substituent on S–E bond length, S–E–S bond angle, and torsion
angle between ES2 and the plane of the central aryl ring of dithiolatotetrylenes owing to London dispersion forces102. ArMe6 = C6H3-
2,6(C6H2-2,4,6‑Me3)2; Ari-Pr4 = C6H3-2,6(C6H3-2,6-iPr2)2; Ari-Pr6 = C6H3-2,6(C6H2-2,4,6-iPr3)2; Ari-Pr8 = C6H-2,6(C6H2-2,4,6-iPr3)2-3,5‑Pr2.

8 | ARTICLE NUMBER 0004 | VOLUME 1 www.nature.com/natrevchem

 REVIEWS

E E

E Bond order
Si, Ge, Sn 3
Pb 1
Cr 5

c
b

Carbon Hydrogen Nitrogen Short contacts, probable

London dispersion interaction
Silicon Chromium Copper Iron

Figure 6 | London dispersion force effects in transition and lanthanide metal complexes. aNature | Results of extended
Reviews | Chemistry
transition state–natural orbitals for chemical valence (ETS–NOCV) analysis of the bonding of terphenyl supported dimers
that indicated the crucial effects of London dispersion forces86,128, and the X‑ray crystallographically characterized
structure of Ari-Pr4CrCrAri-Pr4 (REF. 129) showing selected hydrogen atoms where interligand distances are shorter than the
sum of the van der Waals hydrogen radii (≤2.4 Å)50. b | Crystal structure of the two-coordinate Cu(ii) species
Cu[N(SiMe3)Dipp]2 showing selected hydrogen atoms where interligand distances are shorter than the sum of van der
Waals hydrogen radii131. c | Crystal structure of Fe(1‑norbornyl)4 (REFS 135,138) showing London dispersion interactions
between CH2···CH2 moieties136. Hydrogen atoms are omitted for clarity.

The M(ii) compounds are characterized by planar core
geometries with eclipsed structures. The M–N distances
are shortened, and the compounds, especially the nickel
derivative Ni[N(SiMe3)Dipp]2 (REF. 133), have enhanced
stability relative to the corresponding Ni[N(SiMe3)2]2
analogue, which decomposes at room temperature.
Calculations show that the effects of LDFs between
the ligands across the metal stabilize the complexes by
21.1–29.4 kcal mol−1.
The treatment of transition metal halides with organ-
olithium reagents featuring the powerfully reducing
alkyl anion frequently affords products with different
oxidation states. A case in point is the 1972 synthesis
of the norbornyl complexes M(1‑nor)4 (M = Ti, V, Cr,
Mn, Fe or Co; 1‑nor = bicyclo[2.2.1]hept‑1‑yl), which
feature metals in the unusually high 4+ oxidation state
in the case of iron and cobalt 135. Dispersion-corrected
DFT calculations136 indicated that the M–C bonds are
shortened and the complexes are stabilized by dispersion
attractions between the 1‑norbornyl ligands (FIG. 6c). For
the iron complex, these effects resulted in a calculated
stabilization of 45.9 kcal mol−1, indicating that the degree
of stabilization from dispersion energies is key in deter-
mining the structure and stability of these complexes,
and driving the disproportionation from the salts of
metals in the lower oxidation state.
The behaviour discussed above is not unique to the
metals of the d block; reaction of the bulky cyclopenta-
diene [(4‑nBu-C6H4)5C5H] (abbreviated as CpBIGH) with
Ln(iii) tribenzyl species (Ln = Yb or Sm) gives sponta-
neous reduction to Lnii(CpBIG)2 — reactivity that was
attributed to the presence of a weakly-bound C–H···C
(π) hydrogen-bonding network137. Reaction of this
ligand with a related system also suggests the importance

NATURE REVIEWS | CHEMISTRY VOLUME 1 | ARTICLE NUMBER 0004 | 9

REVIEWS

Box 2 | Characteristic signs of the existence of significant LDF effects in molecular species

• High stability of compounds despite lengthened bonds62

• Sterically counterintuitive structures102
• Lack of expected correlations of various structural parameters79
• Isomerization to different forms to maximize dispersive interactions94,104–107
• Tendency to display spontaneous disproportionation131,135,136,139
• Counterintuitive effects on equilibrium constants82,84
• Isolability of electronically disfavoured molecules58,61
• Well-defined products from dispersion stabilized structures with conservation of dispersion92
• Increased reactivity for catalytic centres with more sterically demanding substituents124,126
• Apparent mutual attraction of rigid multicyclic groups within molecules22,23,57
LDF, London dispersion force.

of these forces in this Schlenk-type equilibrium.
Reaction of the corresponding dibenzylcalcium species
with equimolar CpBIGH does not yield the sterically
expected heteroleptic species but instead gives half
an equivalent of Ca(CpBIG)2 and half an equivalent of
dibenzyl starting material.
Conclusions
LDFs are always present in molecular species. However,
chemists have only recently realized that such forces
can considerably influence the stability, structure and
reactivity of inorganic and organometallic derivatives
bearing sterically large substituents. Until now, recog-
nizing the importance of these forces has come mainly
from post-hoc rationalizations of LDF effects (BOX 2).
By contrast, the designed incorporation of disper-
sion force effects into inorganic and organo­metallic
molecules to alter their stability, structure or reactivity
has not yet occurred, except in a handful of examples131.
Despite the growing number of computational studies
focused on the understanding of LDF effects on sterically
crowded compounds, there are still many experimen-
tally described systems where these effects need compu-
tational authentication. The use of both computational
and experimental methods to incorporate LDF effects
into ligand design should permit a considerable expan-
sion in the range of known classes of compounds and
chemical behaviour.

1. Tang, K.‑T. & Toennies, J. P. Johannes Diderik van der
Waals: a pioneer in the molecular sciences and nobel
prize winner in 1910. Angew. Chem. Int. Ed. 49,
9574–9579 (2010).
2. London, F. Zur Theorie und Systematik der
Molekularkräfte. Z. Physik. 63, 245 (1930); English
translation available in London, F. The general theory
of molecular forces. Trans. Faraday Soc. 33, 8b–26
(1937).
3. Parsegian, V. A. in Van der Waals Forces: A Handbook
for Biologists, Chemists, Engineers, and Physicists
(Cambridge Univ. Press, 2005).
4. Eisenschitz, R. & London, F. Über das Verhältnis der
van der Waalsschen Kräfte zu den homöopolaren
Bindungskräften. Z. Phys. 60, 491–527 (in German)
(1930).
5. Pace, N. C., Scholtz, J. M. & Grimsley, G. R. Forces
stabilizing proteins. FEBS Lett. 588, 2177–2184
(2014).
6. Biedermann, F. & Schneider, H.‑J. Experimental
binding energies in supramolecular complexes. Chem.
Rev. 116, 5216–5300 (2016).
7. Mosher, H. S. & Tidwell, T. T. Frank C. Whitmore and
steric hindrance: a duo of centennials. J. Chem. Educ.
67, 9–14 (1990).
8. Newman, M. S. Steric Effects in Organic Chemistry
(Wiley, 1956).
9. Power, P. P. Some highlights from the development
and use of bulky monodentate ligands. J. Organomet.
Chem. 689, 3904–3919 (2004).
10. Clyburne, J. A. C. & McMullen, N. Unusual structures
of main group organometallic compounds containing
m‑terphenyl ligands. Coord. Chem. Rev. 210, 73–99
(2000).
11. Twamley, B., Haubrich, S. T. & Power, P. P. in Advances
in Organometallic Chemistry Vol. 44 1–65 (Academic
Press, 1999).
12. Ni, C. & Power, P. P. in Metal–Metal Bonding Vol. 136
(ed. Parkin, G.) 59–111 (Springer, 2010).
13. Arduengo, A. J. III Looking for stable carbenes: the
difficulty in starting anew. Acc. Chem. Res. 32,
913–921 (1999).
14. Bourissou, D., Guerret, O., Gabbai, F. P. &
Bertrand, G. Stable carbenes. Chem. Rev. 100, 39–92
(2000).
15. Valente, C. et al. Complexes for the most-challenging
cross-coupling reactions. Angew. Chem. Int. Ed. 51,
3314–3332 (2012).
16. Scott, N. M. & Nolan, S. P. Stabilization of
organometallic species achieved by the use of
N‑heterocyclic carbene (NHC) ligands. Eur. J. Inorg.
Chem. 18, 5–1828 (2005).
17. Asay, M., Jones, C. & Driess, M. N‑Heterocyclic
carbene analogues with low-valent group 13 and
group 14 elements: syntheses, structures, and
reactivities of a new generation of multitalented
ligands. Chem. Rev. 111, 354–396 (2011).
18. Jones, C. Bulky guanidinates for the stabilization of
low oxidation state metallacycles. Coord. Chem. Rev.
254, 1273–1289 (2010).
19. Edelmann, F. T. in Advances in Organometallic
Chemistry Vol. 57 (eds hill, F. E. & Fink, M. J.)
183–352 (Academic Press, 2008).
20. Mindiola, D. J., Holland, P. L. & Warren, T. H. in
Inorganic Syntheses (ed. Rauchfuss, T. B.) (Wiley,
2010).
21. Bourget-Merle, L., Lappert, M. F. & Severin, J. R. The
chemistry of β‑diketiminatometal complexes. Chem.
Rev. 102, 3031–3066 (2002).
22. Schreiner, P. R. et al. Overcoming lability of extremely
long alkane carbon–carbon bonds through dispersion
forces. Nature 477, 308–311 (2011).
23. Fokin, A. A. et al. Stable alkanes containing very long
carbon–carbon bonds. J. Am. Chem. Soc. 134,
13641–13650 (2012).
24. Grimme, S. & Schreiner, P. R. Steric crowding can
stabilize a labile molecule: solving the
hexaphenylethane riddle. Angew. Chem. Int. Ed. 50,
12639–12642 (2011).
25. Echeverría, J., Aullón, G., Danovich, D., Shaik, S. &
Alvarez, S. Dihydrogen contacts in alkanes are subtle
but not faint. Nat. Chem. 3, 323–330 (2011).
26. Pyykkö, P. Strong closed-shell interactions in inorganic
chemistry. Chem. Rev. 97, 597–636 (1997).
27. Brandenburg, J. G., Hocheim, M., Bredow, T. &
Grimme, S. Low-cost quantum chemical methods for
noncovalent interactions. J. Phys. Chem. Lett. 5,
4275–4284 (2014).
28. Fey, N., Ridgway, B. M., Jover, J., McMullin, C. L. &
Harvey, J. N. Organometallic reactivity: the role of
metal–ligand bond energies from a computational
perspective. Dalton Trans. 40, 11184–11191 (2011).
29. Grimme, S. Accurate description of van der Waals
complexes by density functional theory including
empirical corrections. J. Comput. Chem. 25,
1463–1473 (2004).
30. Grimme, S. Semiempirical GGA-type density
functional constructed with a long-range dispersion
correction. J. Comput. Chem. 27, 1787–1799
(2006).
31. Alrichs, R., Penco, R. & Scoles, G. Intermolecular
forces in simple systems. Chem. Phys. 19, 119–130
(1977).
32. Becke, A. D. & Johnson, E. R. A density-functional
model of the dispersion interaction. J. Chem. Phys.
123, 154101 (2005).
33. Jurečka, P., Černy, J., Hobza, P. & Salahub, D. R.
Density functional theory augmented with an empirical
dispersion term. Interaction energies and geometries
of 80 noncovalent complexes compared with ab initio
quantum mechanics calculations. J. Comput. Chem.
28, 555–569 (2007).
34. Zhao, Y. & Truhlar, D. G. Density functionals with
broad applicability in chemistry. Acc. Chem. Res. 41,
157–167 (2008).
35. Zhao, Y. & Truhlar, D. G. Applications and validations
of the Minnesota density functionals. Chem. Phys.
Lett. 502, 1–13 (2011).
36. Johnson, E. R. & Becke, A. D. Van der Waals
interactions from the exchange hole dipole moment:
application to bio-organic benchmark systems.
J. Chem. Phys. Lett. 432, 600–603 (2006).
37. Becke, A. D. & Johnson, E. R. A unified density-
functional treatment of dynamical, nondynamical, and
dispersion correlations. J. Chem. Phys. 127, 124108
(2007).

10 | ARTICLE NUMBER 0004 | VOLUME 1 www.nature.com/natrevchem


38. Ruszinsky, A., Perdew, J. P. & Csonka, G. J. A simple
but fully nonlocal correction to the random phase
approximation. J. Chem. Phys. 134, 114110 (2011).
39. Eshuis, H., Yarkony, J. & Furche, F. Fast computation of
molecular random phase approximation correlation
energies using resolution of the identity and imaginary
frequency integration. J. Chem. Phys. 132, 234114
(2010).
40. Furche, F. & Perdew, J. P. The performance of
semilocal and hybrid density functionals in 3d
transition-metal chemistry. J. Chem. Phys. 124,
044103 (2006).
41. Jiménez-Hoyos, C. A., Janesko, B. G. & Scuseria, G. E.
Evaluation of range-separated hybrid and other
density functional approaches on test sets relevant for
transition metal-based homogeneous catalysts.
J. Phys. Chem. A. 113, 11742–11749 (2009).
42. Ryde, U., Mata, R. A. & Grimme, S. Does DFT‑D
estimate accurate energies for the binding of ligands
to metal complexes? Dalton Trans. 40, 11176–11183
(2011).
43. Swart, M., Solá, M. & Bickelhaupt, F. M. Inter- and
intramolecular dispersion interactions. J. Comput.
Chem. 32, 1117–1127 (2011).
44. Yang, L., Adam, C., Nichol, G. S. & Cockroft, S. L. How
much do van der Waals dispersion forces contribute to
molecular recognition in solution? Nat. Chem. 5,
1006–1010 (2013).
45. Hansen, A. et al. The thermochemistry of london
dispersion-driven transition metal reactions: getting
the ‘right answer for the right reason’. ChemistryOpen
3, 177–189 (2014).
46. Kronik, L. & Tkatchenko, A. Understanding molecular
crystals with dispersion-inclusive density functional
theory: pairwise corrections and beyond. Acc. Chem.
Res. 47, 3208–3216 (2014).
47. Berland, K. et al. I. van der Waals forces in density
functional theory: a review of the vdW‑DF method.
Rep. Prog. Phys. 78, 066501 (2015).
48. Grimme, S. in The Chemical Bond: Chemical Bonding
Across the Periodic Table (eds Frenking, G. & Shaik, S.)
477–500 (Wiley, 2014).
49. Grimme, S., Hansen, A., Brandenburg, J. G. &
Bannwarth, C. Dispersion-corrected mean-field
electronic structure methods. Chem. Rev. 116,
5105–5154 (2016).
50. Bondi, A. Van der Waals volumes and radii. J. Phys.
Chem. 68, 441–451 (1964).
51. Gomberg, M. Triphenylmethyl, ein Fall von
dreiwerthigem Kohlenstoff. Ber. Dtsch. Chem. Ges. 33,
3150–3163 (in German) (1900).
52. Gomberg, M. An instance of trivalent carbon:
triphenylmethyl. J. Am. Chem. Soc. 22, 757–771
(1900).
53. Lankamp, H., Nauta, W. Th. & MacLean, C. A new
interpretation of the monomer-dimer equilibrium of
triphenylmethyl- and alkylsubstituted-diphenyl methyl-
radicals in solution. Tetrahedron Lett. 9, 249–254
(1968).
54. Stein, M., Winter, W. & Rieker, A. Hexakis(2,6‑di‑tert-
butyl‑4‑biphenylyl)ethane — the first unbridged
hexaarylethane. Angew. Chem. Int. Ed. Engl. 17,
692–694 (1978).
55. Kahr, B., van Engen, D. & Mislow, K. Length of the
ethane bond in hexaphenylethane and its derivatives.
J. Am. Chem. Soc. 108, 8305–8307 (1986).
56. Wagner, J. P. & Schreiner, P. R. London dispersion in
molecular chemistry — reconsidering steric effects.
Angew. Chem. Int. Ed. 54, 12274–12296 (2016).
57. Schwertfeger, H., Fokin, A. A. & Schreiner, P. R.
Diamonds are a chemist’s best friend: diamondoid
chemistry beyond adamantane. Angew. Chem. Int. Ed.
47, 1022–1036 (2008).
58. Maier, G., Pfriem, S., Schäfer, R. & Mausch, R. Tetra-
tert-butyltetrahedrane. Angew. Chem. Int. Ed. 17,
520–521 (1978).
59. Balci, M., McKee, M. & Schleyer, P. v. R. Theoretical
study of tetramethyl- and tetra-tert-butyl-substituted
cyclobutadiene and tetrahedrane. J. Phys. Chem. 104,
1246–1255 (2000).
60. Monteiro, N. K. V., de Oliveira, J. F. & Firme, C. L.
Stability and electronic structures of substituted
tetrahedranes, silicon and germanium parents — a
DFT, ADMP, QTAIM and GVB study. New. J. Chem. 38,
5892–5904 (2014).
61. Nemirowski, A., Reisenauer, H. P. & Schreiner, P. R.
Tetrahedrane — dossier of an unknown. Chem. Eur. J.
12, 7411–7420 (2006).
62. Wiberg, N. Sterically overloaded supersilylated main
group elements and main group element clusters.
Coord. Chem. Rev. 163, 217–252 (1997).
NATURE REVIEWS | CHEMISTRY
63. Schäfer, A., Weidenbruch, M., Peters, K. & von
Schnering, H. Hexa-tert-butylcyclotrisilane, a strained
molecule with unusually long Si–Si and Si–C bonds.
Angew. Chem. Int. Ed. 23, 302–303 (1984).
64. Wiberg, N., Schuster, A., Simon, A. & Peters, K.
Hexa-tert-butyldisilane — the molecule with the
longest Si–Si bond. Angew. Chem. Int. Ed. 25, 79–80
(1986).
65. Pyykkö, P. & Atsumi, M. Molecular single-bond
covalent radii for elements 1–118. Chem. Eur. J. 15,
186–197 (2008).
66. Pauling, L. Nature of the Chemical Bond 239 (Cornell
Univ. Press, 1960).
67. Paolini, J. P. The bond order–bond length
relationship. J. Comput. Chem. 11, 1160–1163
(1990).
68. Bock, H., Meuret, J. & Ruppert, K. Sterically
overcrowded or charge perturbed molecules: XXIII.
Hexakis(trimethylsilyl)disilane: structure and
photoelectron spectrum of a sterically overcrowded
molecule. J. Organomet. Chem. 445, 19–28
(1993).
69. Weidenbruch, M. et al. Hexa‑t‑butyldigerman und
Hexa‑t‑butylcyclotrigerman: moleküle mit den derzeit
längsten Ge–Ge− und Ge–C‑Bindungen.
J. Organomet. Chem. 341, 335–343 (in German)
(1988).
70. Puff, H. et al. Bindungsabstände zwischen
organylsubstituierten Zinnatomen: III. Offenkettige
Verbindungen. J. Organomet. Chem. 363, 265–280
(in German) (1989).
71. Wiberg, N. et al. Tetrasupersilyl-tristannaallene and
-tristannacyclopropene (tBu3Si)4Sn3 — isomers with
the shortest S=Sn double bonds to date. Eur. J. Inorg.
Chem. 1999, 1211–1218 (1999).
72. Peng, Y. et al. Substituent effects in ditetrel alkyne
analogues: multiple versus single bonded isomers.
Chem. Sci. 1, 461–468 (2010).
73. Wiberg, N., Amelunxen, K., Blank, T., Nöth, H. &
Knizek, J. Tetrasupersilyldialuminum [(t‑Bu)3Si]2Al–
Al[Si(t‑Bu)3]2: the dialane(4) with the longest Al–Al
bond to date. J. Organometallics 17, 5431–5433
(1998).
74. Uhl, W. Tetrakis[bis(trimethylsilyl)methyl]dialan(4),
eine Verbindung mit Aluminium–Aluminium-Bindung.
Z. Naturforsch. B 43, 1113–1118 (in German)
(1988).
75. Wehmschulte, R. J. et al. Reduction of a
tetraaryldialane to generate Al–Al π-bonding. Inorg.
Chem. 32, 2983–2984 (1993).
76. Wiberg, N. et al. Ditrielanes (R3Si)2E–E(SiR3)2 and
heterocubanes (R3Si)4E4Y4 (R3Si = tBu3Si, tBu2PhSi;
E = Al, Ga, In, Tl; Y = O, Se). Eur. J. Inorg. Chem.
341–350 (2002).
77. Wiberg, N. et al. Tris(tri-tert-butylsilyl)digallanyl
(tBu3Si)3Ga2: a new type of compound for a heavy
group 13 element. Angew. Chem. Int. Ed. 36,
1213–1215 (1997).
78. Power, P. P. π‑Bonding and the lone pair effect in
multiple bonds between heavier main group elements.
Chem. Rev. 99, 3463–3503 (1999).
79. Fischer, R. C. & Power, P. P. π‑Bonding and the lone
pair effect in multiple bonds involving heavier main
group elements: developments in the new millennium.
Chem. Rev. 110, 3877–3923 (2010).
80. Arp, H., Baumgartner, J., Marschner, C., Zark, P. &
Müller, T. Dispersion energy enforced dimerization of a
cyclic disilylated plumbylene. J. Am. Chem. Soc. 134,
6409–6415 (2012).
81. Weidenbruch, M., Kilian, H., Peters, K., von
Schnering, H. G. & Marsmann, H. Compounds of
germanium and tin, 16. A tetraaryldistannene with a
long tin–tin multiple bond and differing environments
at the tin atoms. Chem. Ber. 128, 983–985 (1995).
82. Guo, J.‑D., Liptrot, D. J., Nagase, S. & Power, P. P. The
multiple bonding in heavier group 14 element alkene
analogues is stabilized mainly by dispersion force
effects. Chem. Sci. 6, 6235–6244 (2015).
83. Lee, V. Ya. et al. (tBu2MeSi)2SnSn(SiMetBu2)2: a
distannene with a >Sn=Sn< double bond that is
stable both in the solid state and in solution. J. Am.
Chem. Soc. 128, 11643–11651 (2006).
84. Guo, J.‑D., Nagase, S. & Power, P. P. Dispersion force
effects on the dissociation of ‘Jack‑in‑the-box’
diphosphanes and diarsanes. Organometallics 34,
2028–2033 (2015).
85. Hinchley, S. L. et al. Spontaneous generation of stable
pnictinyl radicals from ‘Jack‑in‑the-box’ dipnictines: a
solid-state, gas-phase, and theoretical investigation of
the origins of steric Stabilization. J. Am. Chem. Soc.
123, 9045–9053 (2001).
REVIEWS
86. Seidu, I., Seth, M. & Ziegler, T. Role played by
isopropyl substituents in stabilizing the putative triple
bond in ArʹEEArʹ[E = Si, Ge, Sn; Arʹ = C6H3‑2,6-
(C6H3‑2,6‑Pri2)2] and Ar*PbPbAr* [Ar* = C6H3‑2,6-
(C6H2‑2,4,6‑Pri3)2]. Inorg. Chem. 52, 8378–8388
(2013).
87. Stender, M., Phillips, A. D., Wright, R. J. & Power, P. P.
Synthesis and characterization of a digermanium
analogue of an alkyne. Angew. Chem. Int. Ed. 41,
1785–1787 (2002).
88. Phillips, A. D., Wright, R. J., Olmstead, M. M. &
Power, P. P. Synthesis and characterization of
2,6‑Dipp2‑H3C6SnSnC6H3‑2,6‑Dipp2
(Dipp = C6H3‑2,6‑Pri2): a tin analogue of an alkyne.
J. Am. Chem. Soc. 124, 5930–5931 (2002).
89. Pu, L., Twamley, B. & Power, P. P. Synthesis and
characterization of 2,6‑Trip2H3C6PbPbC6H3‑2,6‑Trip2
(Trip = C6H2‑2,4,6‑i-Pr3): a stable heavier group 14
element analogue of an alkyne. J. Am. Chem. Soc.
122, 3524–3525 (2000).
90. Mitoraj, M., Michalak, A. & Ziegler, T. A. Combined
charge and energy decomposition scheme for bond
analysis. J. Chem. Theor. Comput. 5, 962–975 (2009).
91. Wu, L.‑C., Jones, C., Stasch, A., Platts, J. A. &
Overgaard, J. Non-nuclear attractor in a molecular
compound under external pressure. Eur. J. Inorg.
Chem. 32, 5536–5540 (2014).
92. Wagner, J. P. & Schreiner, P. R. London dispersion
decisively contributes to the thermodynamic stability
of bulky NHC-coordinated main group compounds.
J. Chem. Theor. Comp. 12, 231–237 (2016).
93. Hänninen, M., Pal, K., Day, B. M., Pugh, T. &
Layfield, R. A three-coordinate iron–silylene complex
stabilized by ligand–ligand dispersion forces. Dalton
Trans. 45, 11301–11305 (2016).
94. Albers, L., Rathjen, S., Baumgartner, J., Marschner, C.
& Müller, T. Dispersion-energy-driven Wagner–
Meerwein rearrangements in oligosilanes. J. Am.
Chem. Soc. 138, 6886–6892 (2016).
95. Andersen, R. A. et al. The molecular structures of
bis(pentamethylcyclopentadienyl)-calcium and
-ytterbium in the gas phase; two bent metallocenes.
J. Organomet. Chem. 312, C49–C52 (1986).
96. Andersen, R. A., Blom, R., Boncella, J. M., Burns, C. J.
& Volden, H. V. The thermal average molecular
structures of bis(pentamethylcyclopentadienyl)
magnesium(ii), -calcium(ii) and -ytterbium(ii) in the
gas phase. Acta Chem. Scand. 41A, 24–35 (1987).
97. Andersen, R. A., Blom, R., Burns, C. J. & Volden, H. V.
Synthesis and thermal average gas phase molecular
structures of bis(pentamethylcyclopentadienyl)-
strontium and -barium; the first organo-strontium and
-barium structures. J. Chem. Soc., Chem. Commun.
768–769 (1987).
98. Blom, R., Faegri, K. Jr & Volden, H. V. Molecular
structures of alkaline earth-metal metallocenes:
electron diffraction and ab initio investigations.
Organometallics 9, 372–379 (1990).
99. Williams, R. A., Hanusa, T. P. & Huffman, J. C.
Structures of ionic decamethylmetallocenes:
crystallographic characterization of
bis(pentamethylcyclopentadienyl)calcium and -barium
and a comparison with related organolanthanide
species. Organometallics 9, 1128–1134 (1990).
100. Hollis, T. K., Burdett, J. K. & Bosnich, B. Why are
bis(pentamethylcyclopentadienyl) complexes, [MCp2*],
of calcium, strontium, barium, samarium, europium,
and ytterbium bent? Organometallics 12,
3385–3386 (1993).
101. Timofeeva, T. V., Lii, J.‑H. & Allinger, N. L. Molecular
mechanics explanation of the metallocene bent
sandwich structure. J. Am. Chem. Soc. 117,
7452–7459 (1995).
102. Rekken, B.‑D. et al. Dispersion forces and
counterintuitive steric effects in main group molecules:
heavier group 14 (Si–Pb) dichalcogenolate carbene
analogues with sub‑90° interligand bond angles.
J. Am. Chem. Soc. 135, 10134 (2013).
103. Eaborn, C. & Smith, J. D. Organometallic compounds
containing tris(trimethylsilyl)methyl or related ligands.
J. Chem. Soc., Dalton Trans. 1541–1552 (2001).
104. Eaborn, C., Hitchcock, P. B., Smith, J. D. &
Sullivan, A. C. Crystal structure of the tetrahydrofuran
adduct of tris(trimethylsilyl)-methyl-lithium, [Li(thf)4]
[Li{C(SiMe3)3}2], an ate derivative of lithium. J. Chem.
Soc., Chem. Commun. 827–828 (1983).
105. Buttrus, N. H. et al. The crystal structure of [(pmdeta)
Li(μ-Cl)Li(pmdeta)][Li{C(SiMe3)3}2]
[pmdeta = Me2N(CH2)2NMe(CH2)2NMe2]. A novel
linear chlorine-centred cation. J. Chem. Soc., Chem.
Commun. 969–970 (1986).
VOLUME 1 | ARTICLE NUMBER 0004 | 11
REVIEWS
106. Al‑Juaid, S. S. et al. Metalation of tris(trimethylsilyl)-
and tris(dimethylphenylsilyl)methane with
methylsodium: the first dialkylsodate. Angew. Chem.
Int. Ed. 33, 1268–1270 (1994).
107. Al‑Juaid, S. S. et al. Crystal structures of organometallic
compounds of lithium and magnesium containing the
bulky ligands C(SiMe3)2(SiMe2X) X = Me, Ph, NMe2, or
C5H4N-2. J. Organomet. Chem. 631, 76–86 (2001).
108. Eaborn, C., Hitchcock, P. B., Smith, J. D. & Sullivan, A. C.
A novel monomeric alkyl–lithium compound. Crystal
structure of [Li{C(SiMe2Ph)3}(tetrahydrofuran)].
J. Chem. Soc., Chem. Commun. 1390–1391 (1983).
109. Eaborn, C., Hitchcock, P. B., Smith, J. D. &
Sullivan, A. C. Preparation and crystal structure of the
tetrahydrofuran adduct of lithium bis
[tris(trimethylsilyl)methyl]cuprate, [Li(THF)4]
[Cu{C(SiMe3)3}2]. The first structural characterization
of a Gilman reagent. J. Organomet. Chem. 263,
c23–c25 (1984).
110. Al‑Juaid, S. S., Eaborn, C., Hitchcock, P. B.,
McGeary, C. A. & Smith, J. D. The crystal structure of
bis{tris(trimethylsilyl)methyl}magnesium: an example
of two‑co‑ordinate magnesium in the solid state.
J. Chem. Soc., Chem. Commun. 1989, 273–274
(1989).
111. Al‑Juaid, S. S. et al. Preparation, crystal structure, and
reactivity of bis {tris(trimethylsilyl) methyl}
magnesium. J. Organomet. Chem. 480, 199–203
(1994).
112. Eaborn, C. & Hitchcock, P. B. The first structurally
characterised solvent-free ς‑bonded diorganocalcium,
Ca[C(SiMe3)3]2. Chem. Commun. 1961–1962 (1997).
113. Westerhausen, M., Rademacher, B. & Poll, W.
Trimethylsilyl-substituierte Derivate des Dimethylzinks
— Synthese, spektroskopische Charakterisierung und
Struktur. J. Organomet. Chem. 421, 175–188
(in German) (1991).
114. Eaborn, C., Jones, K. L., Smith, J. D. & Tavakkoli, K.
The remarkable thermal stability of
benzyl[tris(dimethylphenylsily)methyl]mercury.
How can a bulky ligand stabilize an organometallic
compound towards unimolecular dissociation?
J. Chem. Soc., Chem. Commun. 1201–1202 (1989).
115. Al‑Juaid, S. S., Eaborn, C., Lickiss, P. D., Smith, J.
Davis, Tavakkoli, K. & Webb, A. D. Preparation,
spectroscopic properties and thermal stabilities of
organomercury compounds containing the bulky
ligand (Me3Si)3C or (PhMe2Si)3C. J. Organomet. Chem.
510, 143–151 (1996).
116. Ghotra, J. S., Hursthouse, M. B. & Welch, A. J.
Three‑co‑ordinate scandium(iii) and europium(iii);
crystal and molecular structures of their
trishexamethyldisilylamides. J. Chem. Soc., Chem.
Commun. 6, 9–670 (1973).
12 | ARTICLE NUMBER 0004 | VOLUME 1
117. Evans, W. J., Hughes, L. A. & Hanusa, T. P. Synthesis
and crystallographic characterization of an unsolvated,
monomeric samarium bis(pentamethyl­cyclopenta­
dienyl) organolanthanide complex, (C5Me5)2Sm. J. Am.
Chem. Soc. 106, 4270–4272 (1984).
118. Evans, W. J., Forrestal, K. J. & Ziller, J. W. Reaction
chemistry of sterically crowded tris(pentamethylcyclo­
pentadienyl)samarium. J. Am. Chem. Soc. 120,
9273–9282 (1998).
119. Evans, W. J., Hughes, L. A. & Hanusa, T. P. Synthesis
and X‑ray crystal structure of
bis(pentamethylcyclopenta­dienyl) complexes of
samarium and europium: (C5Me5)2Sm and (C5Me5)2Eu.
Organometallics 5, 1285–1288 (1986).
120. Evans, W. J., Gonzales, S. L. & Ziller, J. W. Synthesis
and X‑ray crystal structure of the first
tris(pentamethylcyclopentadienyl)metal complex:
(η5‑C5Me5)3Sm. J. Am. Chem. Soc. 113, 7423–7424
(1991).
121. Ahlquist, M. S. G. & Norrby, P.‑O. Dispersion and
back-donation gives tetracoordinate [Pd(PPh3)4].
Angew. Chem. Int. Ed. 50, 11794–11797 (2011).
122. Lyngvi, E., Sanhueza, I. A. & Schoenebeck, F.
Dispersion makes the difference: bisligated transition
states found for the oxidative addition of Pd(PtBu3)2 to
Ar‑OSO2R and dispersion-controlled chemoselectivity
in reactions with Pd[P(iPr)(tBu2)]2. Organometallics 34,
805–812 (2015).
123. Maseras, F. & Eisenstein, O. Opposing steric and
electronic contributions in OsCl2H2(PPr3i)2. A
theoretical study of an unusual structure. New
J. Chem. 22, 5–9 (1998).
124. Minenkov, Y., Occhipinti, G., Heyndrickx, W. &
Jensen, V. R. The nature of the barrier to phosphane
dissociation from grubbs olefin metathesis catalysts.
Eur. J. Inorg. Chem. 1507–1516 (2012).
125. Minenkov, Y., Singstad, A., Occhipinti, G. &
Jensen, V. R. The accuracy of DFT-optimized
geometries of functional transition metal compounds:
a validation study of catalysts for olefin metathesis
and other reactions in the homogeneous phase.
Dalton Trans. 41, 5526–5541 (2012).
126. Wolters, L. P., Koekkoek, R. & Bickelhaupt, F. M. Role
of steric attraction and bite-angle flexibility in metal-
mediated C–H bond activation. ACS Catal. 5,
5766–5775 (2015).
127. Wolstenholme, D. J., Dobson, J. L. & McGrady, G. S.
Homopolar dihydrogen bonding in main group
hydrides: discovery, consequences, and applications.
Dalton Trans. 44, 9718–9731 (2015).
128. Ndambuki, S. & Ziegler, T. Analysis of the putative
Cr–Cr quintuple bond in ArʹCrCrArʹ
(Arʹ = C6H3‑2,6(C6H3‑2,6‑Pri2)2 based on the
combined natural orbitals for chemical valence and
extended transition state method. Inorg. Chem. 51,
7794–7800 (2012).
129. Nguyen, T. et al. Synthesis of a stable compound with
fivefold bonding between two chromium(i) centers.
Science 310, 844–861 (2005).
130. Power, P. P. Stable two-coordinate, open-shell (d1–d9)
transition metal complexes. Chem. Rev. 112,
3482–3507 (2012).
131. Wagner, C. L. et al. Dispersion-force-assisted
disproportionation: a stable two-coordinate copper(ii)
complex. Angew. Chem. Int. Ed. 55, 10444–10447
(2016).
132. Boynton, J. N. et al. Linear and nonlinear two-
coordinate vanadium complexes: synthesis,
characterization, and magnetic properties of V(ii)
amides. J. Am. Chem. Soc. 135, 10720–10728 (2013).
133. Lin, C.‑Y. et al. Dispersion force stabilized two-
coordinate transition metal–amido complexes of the
–N(SiMe3)Dipp (Dipp = C6H3‑2,6‑Pri2) ligand:
structural, spectroscopic, magnetic, and computational
studies. Inorg. Chem. 52, 13584–13593 (2013).
134. Faust, M. et al. The instability of Ni{N(SiMe3)2}2: a
fifty year old transition metal silylamide mystery.
Angew. Chem. Int. Ed. 54, 12914–12917 (2015).
135. Bower, B. K. & Tennent, H. G. Transition metal
bicyclo[2.2.1]hept‑1‑yls. J. Am. Chem. Soc. 94,
2512–2518 (1972).
136. Liptrot, D. J., Guo, J.‑D., Nagase, S. & Power, P. P.
Dispersion forces, disproportionation and stable high-
valent late transition metal alkyls. Angew. Chem. Int.
Ed. 55, 13655–13659 (2016).
137. Lewis, R. A. et al. Reactivity and Mössbauer
spectroscopic characterization of an Fe(iv) ketimide
complex and reinvestigation of an Fe(iv) norbornyl
complex. Inorg. Chem. 52, 8218–8227 (2013).
138. Byrne, E. K. & Theopold, K. H. Redox chemistry of
tetrakis(1-norbornyl)cobalt. Synthesis and
characterization of a cobalt(v) alkyl and self-exchange
rate of a Co(iii)/Co(iv) couple. J. Am. Chem. Soc. 193,
1282–1283 (1987).
139. Ruspic, C., Moss, J. R., Schürmann, M. & Harder, S.
Remarkable stability of metallocenes with superbulky
ligands: spontaneous reduction of Smiii to Smii. Angew.
Chem. Int. Ed. 47, 2121–2126 (2008).
Acknowledgements
The authors are grateful to the David Parkin Visiting
Professorship at the University of Bath (P.P.P.), the English-
Speaking Union Lindemann Trust Fellowship (D.J.L.), the US
National Science Foundation (CHE‑1565501) and M. Hill for
his generosity, invaluable advice and support.
Competing interests statement
The authors declare no competing interests.
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Subject categories
Physical sciences / Chemistry / Inorganic chemistry / Chemical bond-
ing [URI /639/638/263/910]
Physical sciences / Chemistry / Inorganic chemistry / Organometallic
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ToC blurb

000 London dispersion forces in sterically

crowded inorganic and organometallic
molecules
David J. Liptrot and Philip P. Power
Despite its relative weakness, the London dispersion
force can strongly influence physical and chemical
properties of molecules. This Review highlights
how structure and reactivity of organometallic and
inorganic molecules are greatly affected by the
Carbon Hydrogen Silicon Lithium
cumulative effect of this force.