Electronic and geometric structure

Oxidation state number of d electrons

atomic number - oxidation state = number of electrons
(neutral atom) (electron deficiency)
# electrons - # for preceding noble gas = # d electrons
Fe3+
Cu+

26 - 3 = 23,
_________

23 - 18 = 5
_________

Oxidation state is formal.

Charge is actually distributed over the ligands.
A.-F. Miller, 2008, pg

Coordination
3
Coordination
number

6
A.-F. Miller, 2008, pg

Figure 2.4
Lippard & Berg
Coordination geometries
associated with different
common coordination
numbers.

d-orbital energies
Crichton Figure 2.1: d orbital shapes
Crystal-Field theory: the arrangement of ligands around
the central metal ion determines the energies of the d
orbitals via electrostatic repulsion between metal ion d
electrons and electron density of ligands.
eg
}
gas phase ion
A.-F. Miller, 2008, pg

t2g

dz2, dx2-y2
3/5oct
2/5oct
dxy, dxz, dyz

L
L
L

M
L

L
L

Strong field / weak field

low-spin / high-spin
eg

S=1/2

spin pairing

t2g

Strong field,
Low spin

Weak field,
High spin

L
M

t2g
A.-F. Miller, 2008, pg

S=5/2
eg

L
4

L
L

Different coordination geometries: Ni2+

Td

distortion towards SqPl

Oh

eg

t2g
L

L
A.-F. Miller, 2008, pg

M
L

Crystal field splitting

A.-F. Miller, 2008, pg

Crichton Figure 2.5

Spectrochemical series
Small
I- < Br- < SCN- < S2- < Cl- < NO3- < F- < OH- ~ RCOOH2O ~ RS- < NH3 ~ Im < bpy < CN- < CO
Large
doubles over this series
Mn2+< Ni2+<Co2+<Fe2+<V2+<Fe3+<Co3+<Mn3+<Mo3+<Ru3+<Pd4+
Im = imidazole, bpy = 2,2-bipyridine
ispga rule
of thumb, and exceptions exist.
A.-F.This
Miller, 2008,
7

Problems with crystal field model

The observed spectroelectrochemical series does not agree
with electrostatics as the dominant interaction
between ligands and d electrons. Eg. halides I- and Bshould not be so weak, OH- should not be weaker than
H2O.
When bonding and overlap between orbitals of different
symmetries is taken into account, we obtain ligand field
theory.
bonds are head-on, along the line of a bond.
bonds are side-to-side with electron density above and
below the line of the bond, but with no density on the line.
bonding is more polarizable and allows electron density to
be more
delocalized (lower energy).
A.-F. Miller, 2008, pg
8

Orbitals vs. bond types

Each ligand forms a bond first, eg. with a lone pair.
bonds may be from metal ion d orbitals to ligand p or
orbitals.
bonds can use metal ion s, p. dz2 or dx2-y2. (ligands along
x,y,z)
bonds can be made of metal ion dxy, dxz or dyx orbitals.

A.-F. Miller, 2008, pg

Example MOs produced by the

ligand-field model.
Metal-like: d

Ligand-like
Critchton Figure 2.6
Ligands each donate a PAIR of electrons (and fill an MO).
Metal ion electrons t2g or eg* Retain the FORM of the Xtal field diagram.

A.-F. Miller, 2008, pg

10

Ligand-field effects on
donors

Crichton Fig. 2.7

Lower-E ligand orbitals that are populated. Upon hybridization with t2g , the set
that drop are ligand-like & populated. The metal-like orbitals move to higher E ().

A.-F. Miller, 2008, pg

11

Ligand-field effects on
acceptors

Crichton Fig. 2.7

Higher-E ligand orbitals are vacant. Upon hybridization with t2gs , the set
that drop are metal-like (). They remain vacant. Examples: CN- and CO.
A.-F. Miller, 2008, pg

12

Ligand-field effects on

Crichton Fig. 2.7

Electrostatic repulsion can still raise the energy of any metal electrons in eg*.
NEW: consideration of bonding provides for lowering the energy of the t2g
orbitals.
Full-full interactions or empty-empty interactions have no net effect.
acceptor ligands partially oxidize the metal, stabilize formal low oxidation states.
-, OH-.
donor ligands
stabilize
high
formal
oxidation
states
:
F
A.-F. Miller, 2008, pg
13