1

Molecular Orbital Theory

Wulfsberg Chapter 10

Frontier orbitals
HOMO Highest Occupied Molecular Orbital
LUMO Lowest Unoccupied Molecular Orbital
SOMO Singly Occupied Molecular Orbital
Hardness = = (E
LUMO
-E
HOMO
)
Softness=1/

Some Crystal and Ionic Radii
Ion Charge Coordination Spin State Crystal Radius Ionic Radius
Cr
2 VI
Low Spin 0.87 0.73
High Spin 0.94 0.8
3 VI

0.755 0.615
4
IV

0.55 0.41
VI

0.69 0.55
5
IV

0.485 0.345
VI

0.63 0.49
VIII

0.71 0.57
6
IV

0.4 0.26
VI

0.58 0.44
Fe
2
IV High Spin 0.77 0.63
IV (SQ) High Spin 0.78 0.64
VI Low Spin 0.75 0.61
High Spin 0.92 0.78
VIII High Spin 1.06 0.92
3
IV High Spin 0.63 0.49
V 0.72 0.58
VI Low Spin 0.69 0.55
High Spin 0.785 0.645
VIII High Spin 0.92 0.78
4 VI 0.725 0.585
6 IV 0.39 0.25

Pauling O
2-
(140 pm) Shannon O
2-
(126 pm)
2



Symmetry of octahedral complex with pi-donor / pi-acceptor (p-orbital) ligands
What is relative strength of overlap for d-orbitals in ?

3

Metal-Metal Bonding
Overlap of orbitals between metal atoms can be of several types as shown below.
With different metals we may observe
a) covalent/electron precise bonds - one electron from each metal
b) dative bond - HOMO to LUMO
c) symmetry related weak overlap of bonding/non-bonding /antibonding orbitals

The number of metal-metal bonds is given by the number of d-orbital electrons that participate in
bonding, usually in accordance with the 18-electron rule for each metal.
For the square planar complex shown,
metal-metal bonding is optimum with
four electron pairs giving a quadruple
bond (example [Re
2
Me
8
]
2-
). Short
inter-metal distances are first
indicators of metal bonding.
Questions
1. Would you expect a metal-metal
quadruple bond to be staggered or
eclipsed?
2. Why are only four d-orbitals shown
in the energy level scheme?

4


5

The Lanthanide Contraction
Wulfsberg p34-44

Atomic and Ionic radii depend on screening of outermost
electrons-effective nuclear charge.

The lanthanide atoms and ions become smaller with
increasing number of electrons due to ineffective screening
and shapes of f-orbitals. There are many nodes or direct
paths to the nucleus for outer electrons and the nuclear
charge increases steadily across the series. By the time 14
protons are added there is a sizeable contraction because of
the increase in effective nuclear charge.



Mikami, K.; Terada, M.; Matsuzawa, H. Angew. Chem., Int. Ed. 2002, 41, 3554.

Aqueous Chemistry of the Lanthanides and Actinides
Major applications of the lanthanides are in electronics (sharp electronic transitions of f-electrons) and
as catalysts for organic transformations. Lanthanide complexes afford a wide range of Lewis acids due to
the variations in radii and charge density of the ions.


6

Chiral transformations are also increasingly important:













The Actinides
The elements show wide variation in electronic structure with different oxidation states as may be
expected with the comparable energies of 5f, 6d, 7s, 7p orbitals. An electron can readily transit
between various orbitals with limited energetic demand. Consequently, several cationic species may
coexist in a single solution of a particular actinide, compounding their aqueous chemistry. Nevertheless,
the high oxidation states may be stabilized, as for lower elements, in high concentrations of acid.
Furthermore, the solution chemistry of long lived actinides is dominated by moderately stable 3+
oxidation states and even more stable oxo-cations such as UO
2+
. These oxo-species are important for
industrial separation of the elements from their ores.

7

Host Guest Interactions
Non-Covalent Interactions
1) Repulsive Interactions with orbital overlap of electrons, repulsion occurs over a short
range but increases by r
12
inside van der waals radius.

2) Charge-Charge interactions strong attractive forces between opposite charges, vary by r
2
,
accounts for low vapour pressure of ionic compounds.

3) Dipole Interactions
a) Dipole-Dipole: electronegativity between atoms results in dipoles in molecules that can
combine according to Coulombs law. Decreases with r
3
.
b) Charge-Dipole: similar to above except one molecule has formal positve or negative
charge.
c) Dipole-Induced Dipole: A molecule with a permanent dipole can induce a dipole in a
second molecule that is located nearby in space. The strength of the interaction
depends on the dipole moment of the first molecule and the polarizability of the
second. Pi-electron systems, like benzene, are more polarizable. Dipole-induced dipole
interactions are always attractive and can
contribute as much as 2 kJ/mole to
stabilization.Decrease with r
4
.

d) Fluctuating Dipoles(London or Dispersive Forces): Molecules behave like oscillating
dipoles because of constant movement of electron density. In molecules that are
located nearby to each other the oscillators are coupled. Coupled fluctuating dipoles
experience favorable electrostatic interaction known as dispersive interactions. The
strength of the interaction is related to the polarizabilities of the two molecules.
Dispersive interactions are always attractive and occur between any pair of molecules,
even non-polar molecules. Dispersive interactions provide the only attractive force
between molecules in liquid N
2
, which boils at 77K. For a given atom-atom contact the
energy of stabilization provided by dispersive interactions is very small (0.2 kJ/mole),
but can make a large contribution to stability in large proteins.

4) Hydrogen Bonding- the hydrogen-bonding distance from H to O in water is ~1.8 , which is
less than the sum of the O and H van der Waals radii (O, 1.5 ; H, 1.0 ). The distance from
O to O is around 2.8 , which is less than twice the van der
Waals radius of oxygen (1.5 ). The differences in
electronegativity cause distortion in electron density and
generate postive and negative partial charges. Hydrogen
bonds can also be three-centered and four-centered.

O
+
O
+
8

Solvent, Counter ion, and Entropic effects-large molecules can generate strong radial electric
fields which have to be balanced by a high concentration of counter-ions. For DNA, the
phosphate groups cause 2M concentration of K
+
close to the molecule, irrespective of bulk
concentration, hence the the dramatic salt dependencies of DNA melting and DNA-protein
complexation. In the condensed state, DNA helices are separated by one or two layers of
water. In aqueous solution, highly charged cations such as spermine (+4) or spermidine (+3) are
required to decrease electrostatic repulsion of adjacent negatively charged DNA segments.
Entropy changes also accompany the transitions between DNA and protein states as solvent
molecules are released or adsorbed.

5) Hydophobic Effects: In bulk water, intermolecular forces are isotropic. At the interface with
hydophobic molecules like octane, these forces are anisotropic because the octane
molecule does not form hydrogen bonds. Thus water at the interface is rotationally and
translationally constrained and the entropy of these molecules decreases.









As isolated molecules aggregate in aqueous solution, the total volume of interfacial
water decreases. The driving force for aggregation of hydrophobic substances in
aqueous solution (phase separation) is the increase in entropy of the aqueous phase.
Hydrophobic effects may play a significant role in host guest chemistry as the host may
offer a polar/apolar environment to the guest which is more appropriate than the bulk
solvent.

9







o
o
o
o
o
o o
o
o
o
o
o
NONACTIN
OR
RO
O
O
O
O
O
Alternate Calixarene
O
O
O
O
O O
O
O
O
O
O O
Na
Na
Fe
O
O
O
O
O O
O
O
O
O
O O
Fe
K
S
S
S
S
10










2.8
2.5
N
M
N
109
o
1.6
N
M
N
69
o
2.5
Angles, lengths and bite size in AzaMacrocycles
N
N
NH
2
H
2
N
N N
N N
Log K = 12 Log K = 22
N N
NH HN
Cu
N N
N N
Cu