Topic 4:

d-Block Chemistry

4-1

Required Background

Ground state electronic configuration

Trends in first ionization energy

Metallic radii

Aquated cations: formation and acidic properties

Solubility of ionic salts

Stability constants for metal complexes

Selected ligand structures and abbreviations

Redox chemistry in aqueous solution (potential diagrams)

Geometrical isomerism

Chiral molecules

Binary metal hydrides

4-2

Electronic Configurations

a triad

copper triangle

platinum-group metals

heavier d-block metals

4-3

Trends in Metallic Radii

> little variations across a given row of the d-block

> greater for 2nd and 3rd row metals than for first row metals
> similar for the 2nd and 3rd row metals in a given a triad

4-4

Oxidation States
Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

[0]

[4]

Zn

4-5

Problem 4-1: For each of the following complexes, give the oxidation state of the
metal and its dn configuration:

a) [Mn(CN)6]4

b) [CoCl3(py)3]
c) [Ru(bipy)3](PF6)2
d) [Ni(en)3]2+
e) [Cr(acac)3]
f) [Ti(H2O)6]3+

4-6

Paulings Electroneutrality Principle

The distribution of charge in a molecule or ion is such that the charge on a
single atom is within the range +1 to 1 (ideally close to zero)

> the electroneutrality principle results in a bonding description for the [Co(NH3)6]3+
ion which is 50% ionic and 50% covalent.

4-7

Coordination Numbers
Coordination
Number
2
3
4
5
6
7
8

Common Geometry
linear
trigonal Planar
tetrahedral, square planar
trigonal bipyramidal,
square based pyramidal
octahedral
pentagonal pyramidal
dodecahedral
square antiprismatic
hexagonal bipyramidal
tricapped trogonal prismatic

Less Common Geometry

trigonal pyramidal

trigonal prismatic
monocapped trigonal prismatic
monocapped ocathedral
cube, bicapped trigonal
prismatic

Note: if the energy difference between different structure is small, fluxional behavior
in solution may occur

4-8

VSEPR Theory and Kepert Model

VSEPR theory successfully predicts the shapes of molecular species of the

main group elements,but fails for d-block elements:
[V(H2O)6]3+, [Mn(H 2O)6]2+, [Co(H2O)6]2+, [Ni(H2O)6]2+, [Zn(H2O)6]2+ have
different electron configurations, but identical shape (octahedral)
> the Kepert model rationalizes the shapes of d-block metal complexes by
considering only the repulsions between the ligands:
2
3
4
5
6

linear
trigonal
tetrahedral
trigonal bipyramidal
octahedral

The Kepert model fails for square planar complexes (due to electronic
effects) or inherent constraints of a ligand (e.g. tripodal ligand)

4-9

Problem 4-2: Within the Kepert model, what geometries do you predict for the
following coordination complexes?

a) K4[Mn(CN)6]

b) [Cu(SPMe3)3][BF4]
c) [Ag(NH3)2]+

4-10

Coordination Number Two

Uncommon, generally restricted to Cu(I), Ag(I), Au(I) and Hg(II) (d 10 ions)

Examples:
[CuCl2], [Ag(NH3)2]+
[Au(CN)2], Hg(CN)2

[Au{P(cyclo-C6H11)3}2]+

Note: Bulky ligands generally stabilize coodination numbers

4-11

Coordination Number Three

Usually trigonal planar structures observed, typical for d10 metal centers

Examples:
Cu(I) in [Cu(CN)3]2, [Cu(SPMe3)3]+
Ag(I) in [AgTe7]3, [Ag(PPh3)3]+
Au(I) in [Au{PPh(C6H11)2}3]+
Hg(II) in [Hg(SPh3)3]
Pt(0) in (Pt(PPh3)3]

[AgTe7]3

[Fe{N(SiMe3)2}3]

4-12

Coordination Number Four

Very common, most frequently with tetrahedral geometry

> distortions often due to steric or crystal packing effects

Examples:
d0: [VO4]3, [CrO4]2
d1: [MnO 4]2, [ReO4]2, [RuO4]
d2: [FeO4]2, [RuO4]2
d5: [FeCl4], [MnCl4]2
d6: [FeCl4]2
d7: [CoCl4]2
d8: [NiCl4]2, [NiBr4]2
d9: [CuCl4]2
d10: [ZnCl4]2, [CdCl4]2, [Cu(CN)4]3, [Ni(CO)4]

[Rh(PMe2Ph)4]+

Transition metals with d8 configuration strongly favor a square planar

geometry!

4-13

Coordination Number Five

Limiting case: Trigonal pipyramid, square-based pyramid

But: many structures lie between these two extremes (often small energy
difference)

Examples:
d0:

[Cu(bpy){NH(CH2CO2)2}4]

[NbCl4(O)]

d1: [V(acac)2(O], [WCl4(O)]

d2: [TcCl4(O)]

Found for many

polydentate amine or
phosphine ligands:

[Zn{N(CH2CH2NH2)3}Cl]+

Conformational constraint of
ligand gives preference for a
square-based pyramidal complex

4-14

Problem 4-3: Suggest a structure for [CuCl(L)]+, assuming that all donor atoms
are coordinated to the Cu(II) center.

L=

N
N

4-15

Coordination Number Six

Vast majority show octahedral geometry, trigonal prismatic complexes are

very rare

Examples: aqua complexes

[Ti(H2O)6]3+, [V(H2O)6]3+, [Cr(H2O)6]3+, [Mn(H2O)6]2+, [Fe(H2O)6]2+,
[Zn(H2O)6]2+, etc.
Example for a trigonal prismatic
structure:

[Re(S2C2Ph2)3]

Difference between octahedral and

trigonal prismatic geometry:

4-16

Coordination Number Seven

Coordination number 7 or greater are observed most frequently for ions of

the early, second, and third row d-block metals, and for lanthanoids and
actinoids > rcation must be large to accommodate seven or more ligands

[TaCl4(PMe3)3]

[ZrF7]3

[ScCl2(15-crown-5)]+

4-17

Coordination Number Eight

With increasing coordination number also increasing number of possible

structures:

[Nb(ox)4]4

[Y(H2O)8]3+

[CdBr2(18-crown-6)]

4-18

Isomerism in Coordination Complexes

4-19

Structural Isomerism

Ionization isomers: result from the interchange of an anionic ligand within

the first coordination sphere with an anion outside the coordination sphere:
[Co(NH3)5Br][SO4] (violet), and [Co(NH3)5(SO4)]Br (red)

Hydration isomers: result from interchange of H2O and another ligand

between the first coordination sphere and the ligands outside it:
CrCl36H2O: [Cr(H 2O)4Cl2]Cl2H2O, [Cr(H2O)5Cl]Cl2H2O, [Cr(H2O)6]Cl3

Coordination isomers: only possible for salts in which boh cation and anion
are complex ions > the isomers arise from interchange of liagnds between
the two metal centers:
[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]

Linkage isomers: arise when one or more of the ligands can coordinate to
the metal in more than one way, e.g. [SCN] :
[Co(NH3)5(NCSN)]2+ and [Co(NH3)5(NCSS)]2+

4-20

Geometrical Isomerism

Cis- and trans-isomers of a square planar complex can be distinguished by

IR spectroscopy or NMR spectroscopy:
31P NMR of [PtCl (PBu ) :
2
3 2

195Pt(I=1/2)

Note: for an IR active vibration a change in

the molecular dipole moment is required

constitutes 33.8%
> gives rise to satellite peaks
(doublet coupling pattern)
> JPPt (cis) = 3508 hz and
JPPt(trans) = 2380 Hz

4-21

Problem 4-4: In the solid state Fe(CO)5 posses a trigonal bipyramidal structure.
a) How many carbon environments are there?

b) Explain why only one signal is observed in the 13C NMR of Fe(CO)5, even at
low temperature.

4-22

Problem 4-5: Using spectroscopic methods, how would you distinguish between
fac- and mer-[RhCl3(PMe3)3]?

4-23

Optical Isomerism

Simplest case: metal cation surrounded by three identical bidentate ligands,

e.g. [Co(en)3]3+:

> the two isomers are non-superimposable images of each other and
therefore chiral molecules
and prefixes: labels to identify the two enantiomers.
The octahedron is viewed down a 3-fold axis, and the chelate defines
then a right () or left () handed helix.

4-24

Problem 4-6: Comment on the possibility of isomer formation for each of the
following complexes:
a) [Ru(py)3Cl3]

b) [Ru(bipy)2Cl2]+

c) [Ru(tpy)Cl3]

N
N

tpy

4-25

Problem 4-7: State the types of isomerism that may be exhibited by the following
complexes, and draw structures of the isomers.
a) [Co(en)2(ox)]+

b) [Co(en)(NH3)2Cl2]2+

4-26

Bonding in Metal Complexes

Valence bond theory (Pauling, 1930) not much used today, but the concept
is still useful for a qualitative understanding
> hybridization scheme used for main group elements can be also applied
to d-block elements: an empty hybrid orbital on the metal center can accept
a pair of electrons from a ligand to form a -bond.
Example: octahedral complex of Cr(III)
The atomic orbitals required for an octahedral complex are the 3dz2,
3dx2y2, 4s, 4px, 4py, and 4pz
These orbitals must be unoccupied so as to be available to accept six
pairs of electrons from the ligands:
vacant orbitals accept
ligand electrons
3d

4s

4p

hybridization
3d

d2sp3

4-27

Coordination
Number
2
3
4
5
4
5
6
6

Geometry

Orbitals

Linear
Trigonal planar
Tetrahedral
Square planar
Trigonal bipyramidal
Square-based pyramidal
Octahedral
Trigonal prismatic

s, pz
s, px, py
s, px, py, pz
s, px, py, dx2-y2
s, px, py, pz, dz2
s, px, py, pz, dx2-y2
s, px, py, pz, dz2, dx2-y2
s, dxy, dyz, dxz, dz2, dx2-y2

Description

sp
sp2
sp3
sp2d
sp3d
sp3d
sp3d2
sd5

Example

[Ag(NH3)2]+
[HgI3]
[FeBr4]2
[Ni(CN)4]2
[CuCl5]3
[Ni(CN)5]3
[Co(NH3)6]3+
[Mo(S2C2Ph2)3]

4-28

Problem 4-8: Describe the hybridization scheme and electron configuration of the
following complexes:
a) low spin [Fe(CN)6]3

b) high spin [FeF6]3

4-29

Splitting of d-Orbital Energy in Octahedral Complexes

How does the ligand field influence

the energy of the five metal d-orbitals?
y

d z2 d x 2 y 2

Orientation along ligand-metal

bond axis
=> raised to higher energy

d xy d xz d yz

Orientation between ligand-metal

bond axis
=> raised to less higher energy

4-30

Ligand Field Theory

The ligand field is an electrostatic model which predicts the energy splitting
of of the d orbitals in a complex. Ligands are considered point charges, and
there are NO metal-ligand covalent interactions

eg
t2g

Metal ion in
gas phase

Spherical charge
distribution around
metal ion

charge distribution
with octahedral
symmetry around
metal ion

4-31

Octahedral Complexes
orbital
energy
eg

d z2 d x 2 y 2
3/5 oct

2/5 oct
t2g

d xy

d xz

d yz

oct (weak field) < oct (strong field)

oct = 10 Dq

4-32

Field Strength

The splitting energy oct can be determined from spectroscopic data:

max = 20,300 cm1
Example: [Ti(H2O)6]3+:

energy

eg
t2g

4-33

Influence of Ligand

The absorption maximum in Ti(III) complexes is sensitive to the ligand

environment (= field strength).
Since the absorption is due to transition of an electron from the t2g orbitals to the
eg orbitals, the absorption energy corresponds to O.

Ligand

O/cm1

Br

11,400

Cl

13,000

(H2N)2C=O

17,550

NCS

18,400

18,900

H2O

20,100

CN

22,300

4-34

Magnitude of Splitting Energy (O)

Charge on the metal (oxidation state)

For first row transition elements O varies from about 7,500 cm 1 to 12,500 cm1 for
divalent ions, and 14,000 cm1 to 25,000 cm 1 for trivalent ions.

Position in a group
values for analogous complexes of metal ions in a group increases by 25% to 50%
going from one transition series to the next:
[M(NH3)6]3+ with M=Co 23,000cm1, M=Rh 34,000cm1, M=Ir 41,000 cm1

Geometry and coordination number

For identical (or nearly identical) ligands t (tetrahedral) is 4/9 of O. This is a result
of the reduced number of ligands and their orientation relative to the d orbitals.
Note: The energy ordering of the orbitals is reversed in tetrahedral complexes
relative to that in octahedral complexes.

Identity of ligand
The dependence of on the nature of the ligand follows an empirical order, known
as the spectrochemical series, for all metals in all oxidation states and geometries.

4-35

Spectrochemical Series

Order of ligand field strength with decreasing Dq:

CN > phen ~ NO2 > en > NH3 ~ py > H3O > C2O42 > OH > F > S2 > Cl
> Br > I
Note: H2O > OH: this cannot be explained in terms of the electrostatic model

Order of metals with increasing Dq:

Mn(II) < Ni(II) < Co(II) < Fe(III) < Cr(III) < Co(III)
< Ru(III) < Mo(III) < Rh(III) < Pd(II) < Ir(III) < Pt(IV)

4-36

Estimation of Splitting Energies

10 Dq ~ f (ligand) g (metal)
Ligand

f factor

Metal ion

g factor [1000 cm1]

Br
SCN
Cl
N3
F
C2O4
H2O
NCS
gly
py
NH3
en
bpy
CN

0.72
0.73
0.78
0.83
0.90
0.99
1.0
1.02
1.18
1.23
1.25
1.28
1.33
1.70

Mn(II)
Ni(II)
Co(II)
V(II)
Fe(III)
Cr(III)
Co(III)
Ru(II)
Mn(IV)
Mo(III)
Rh(III)
Tc(IV)
Ir(III)
Pt(IV)

8.0
8.7
9.0
12
14
17.4
18.2
20
23
24.6
27.0
30
32
36

4-37

Problem 4-9: Estimate the splitting energy oct for the following octahedral
complexes:
a) [Cr(NH3)6]3+

b) [Co(en)2Cl2]+

4-38

Ligand Field Stabilization Energy (LFSE)

Example: [Cr(NH3)6]3+
energy

=> octahedral complex, d 3 electron configuration

LFSE = 3 (4) Dq = 12 Dq

d z2 d x 2 y 2
6 Dq

O = 10 Dq

4 Dq

d xy

d xz

d yz

Note: The LFSE for any octahedral complex with d3 electron configuration is 12 Dq,
but the absolute value of Dq varies with ligand and metal!

4-39

Problem 4-10: Calculate the crystal field stabilization energy (in cm1) for
[Co(NH3)6]2+. (oct = 10,200 cm 1)

4-40

Influence of Splitting Energy

[Cr(CN)6]4

[CrCl6]4
oct < SPE

oct > SPE

energy

d z2 d x 2 y 2
6 Dq

d z2 d x 2 y 2
6 Dq

4 Dq

d xy

d xz

stronger
field

4 Dq

d yz
d xy

LFSE = 6 Dq + 3(4 Dq) = 6 Dq

d xz

d yz

LFSE = 4(4) Dq = 16 Dq

4-41

Spin State and Ligand Field Strength

4-42

Ligand Field Stabilization Energies

4-43

Splitting Energies for Aqueous Complexes

= Spin pairing energy

Note: Only Co3+ has a splitting energy similar to the spin pairing energy
> It is the only low-spin aqua complex of the listed examples!

4-44

Low-Spin vs. High-Spin Complexes

Strong-field ligands = low-spin complexes

Strong field ligands have pi-acceptor orbitals or low-lying d-orbitals:
* as in CO or CN, * as in CH2=CH2, low lying d as in PR3, PF3

Weak field ligands = high-spin complexes

Weak field ligands have pi-donor orbitals:
Usually multiple p-orbitals as in X
Intermediate field ligands = usually high-spin for +2 ions, low-spin for
+3 ions
Intermediate field ligands have few, or no pi-donor or acceptor orbitals, or
there is a poor match in energy of available pi-orbitals: NH3, H2O, pyridine
Note:
Complex stability and reactivity do not necessarily correlate with ligand field
strength
> Thermodynamic stability refers to the energetics of a given reaction
> Kinetic stability (=reactivity) refers to the rate with which a given reaction
occurs (activation energy)

4-45

Molecular Orbital Theory: Octahedral Complexes

Complexes with s-bonding only (e.g. [Co(NH3)6]3+:

Note: in a complex without p-bonding, the difference

between eg* and t2g corresponds to the splitting energy oct

4-46

Effect of pi-donor/acceptor interactions

energy
eg

eg
O

eg
O

t2g

t2g
t2g
sigma bonding
only

sigma +pi
donor

sigma + pi
acceptor

intermediate field
ligands

low field ligands

high field ligands

4-47

Cyanide is a Pi-Acceptor
MO-Diagram of CN

energy

Overlap of d, *, and p-orbitals with

metal d orbitals:
>Overlap is good with ligand d and
p *-orbitals, poorer with ligand porbitals

4-48

-donor ligands

-acceptor ligands

4-49

Effect of pi-Bonding
energy

4-50

Jahn-Teller Distortion

Octahedral complexes of d9 and high-spin d4 ions are often distorted (axial

bonds are different in lengths compared to equatorial bonds)
> system of lower symmetry with non-degenerate orbitals is more stable

d z2 d x 2 y 2
6 Dq

dx 2 y 2

+1/2

d z2

1/2

6 Dq

elongation

d xy

4 Dq

4 Dq

+2/3
1/3

d xy

d xz

d yz

d xz d yz

L
L

L
L

4-51

Problem 4-11: Which of the following complexes exhibit a distorted octahedral

geometry. Determine, whether the distortion is due to elongation or contraction
along the axial molecule axis.
a) [Cu(NH3)6]2+

b) [Cr(NH3)6]3+

c) [Ti(H2O)6]3+

4-52

Tetrahedral Complexes
orbital
energy
t2

d xy

d xz

d yz

2/5 tett
tet = 10 Dq

3/5 tet
e

d z2 d x 2 y 2
tet = 4/9 oct

4-53

Tetrahedral Complexes

least ligand-ligand repulsion

Small ligand field splitting energy (only four ligands, and they are not aligned along
the orbital axis)
> the ligand field splitting energy is in most cases too small to overcome the spin
pairing energy, therefore tetrahedral low spin complexes are very rare!
Ideal geometry for metal cations with no LFSE (d0, d5 and d10), or only little
LFSE (d2, d7)
Examples: MnO4 (d0), FeO42 (d2), FeCl4 (d5, high spin)
CoCl42 (d7, high spin), ZnCl42 (d10)
NO
Si
Cr[N(SiMe3 )2 ]3 NO

Cr
L

L
A rare example for a low spin complex
with tetrahedral coordination geometry

L=

N
Si

4-54

Removal of z ligands

energy

dx2 y2

dx2y2
d z2

d z2 d x 2 y 2

d xy

d xy
d xy

d yz

d xz

d xz

d z2

d yz
d xz

d yz

4-55

Square Planar Complexes

orbital
energy

dx 2 y2

d xy

d xz

d xy

d yz

d z2

d z2 d x 2 y 2
d xz

d yz

Tetrahedral
[NiCl4]2

Square planar
[Ni(CN)4]2

paramagnetic

diamagnetic

4-56

Square Planar Complexes

Square planar complexes are expected for all metal cations

with d8 electron configuration
> this geometry offers the greatest stabilization according
to the ligand field theory, since the highest energy orbital
dx2-y2 remains unoccupied

energy

dx2 y2

Examples: Ni(II), Pt(II), Pd(II), Au(III)

Square planar complexes with d8 configuration are always

diamagnetic

d xy

Examples: Ni(H2O)62+: octahedral > paramagnetic

d z2

Ni(CN)42: square planar > diamagnetic

Ni(Cl)42: tetrahedral > paramagnetic

d xz

d yz

4-57

Problem 4-12:
a) The anion [Ni(SPh)4]2 is tetrahedral. Explain why this complex is
paramagnetic.

b) The complexes NiCl2(PPh3)2 and PdCl2(PPh3)2 are paramagnetic and

diamagnetic. What dies this tell you about their structures.

4-58

Energy Diagram Overview

4-59

Electronic Spectra

Studies of electronic spectra of metal complexes provide information about

structure and bonding. Absorptions arise from transitions between electronic
energy levels:
Transitions between metal-centered orbitals possessing d-character =
d- d transitions (MC) (weak intensity, Laporte-forbidden)
Transitions between metal- and ligand-centered orbitals = metal-toligand or liagnd-to-metal charge transfer transitions (MLCT, LMCT)
(strong intensity)

Absorption bands are usually broad

due to vibrational and rotational
sublevels

Amax =

max

cl

4-60

Selection Rules

Spin Selection Rule: S = 0

> Transitions may occur from singlet to singlet, or triplet to triplet states
etc., but a change in spin multiplicity is forbidden.

Laporte Selection Rule: l = 1

> There must be a change in parity:
allowed transitions: g u
forbidden transitions: g g and u u
Therefore, allowed transitions are s p, p d, d f,
forbidden transitions are s s, p p, d d, s d, p f

Spin-forbidden transitions can be still observed due to spin-orbit coupling

and vibronic coupling
Charge transfer transitions are allowed by the selection rules and have
therefore greater intensity than d-d transitions

4-61

Problem 4-13:
Explain why [Mn(H2O)6]2+ is very pale in color, but [MnO4] is intensively purple
colored.

4-62

Term Symbols

For multielectron atoms with open shells, there are several (energetically
non-equivalent) possibilities to place the electrons in the orbitals, e.g.:
etc.

The angular momentum and spin multiplicity of an atom is specified by a

symbolic representation:

aT
multiplicity a = 2S+1

S, P, D, F, (L=0, 1, 2, 3)

Atoms in S, P, D, F state have the same angular momentum L, just as for

the H-atom with a single electron in s, p, d, f

The quantum number S is the summation of all electron spins in the atom

Hunds Rule: Ground state has maximum spin multiplicity. If there are two states with
identical multiplicity, the ground state has the highest value of L

4-63

Example: Ground State of Carbon (for details see Box 20.5)

1s2 2s2 2p2
filled shell
=> S = 0 (all spins are paired)
L = 0 (all momentum cancel each other out)
=> only 2p2 must be considered:
n = 2, l = 1
ml = +1, 0, 1
ms = +1/2,1/2

ML = ml (= total angular momentum)

MS = ms (= total spin)

(py, pz, px)

(spin state)

ML = 0, 1, 2, L
MS = S, S1, S2, S

ml

+1

ML

+1

Therefore: L = 1, S = 1 =>

+1

0
3P

is ground state

+1
1

4-64

Problem 4-14: Determine the ground state term for Ti3+ and Co2+.

4-65

Electronic Spectra of Octahedral Complexes

The energy states of a metal cation in a octahedral environment are further

splitted by the ligand field:

Term

Degeneracy

A1g

T1g

Eg + T2g

A2g + T1g + T2g

A1g + Eg + T1g + T2g

11

Eg + T1g + T 1g + T2g

13

A1g + A2g + Eg + T1g + T 2g + T2g

States in octahedral ligand field:

4-66

Electronic Spectra of d1 Complexes

Example: [Ti(H2O)6]3+:
Ground state: 2D => splitting to T2g and Eg in octahedral ligand field:

energy

d z2 d x 2 y 2

d xy

d xz

d yz

d z2 d x 2 y 2

d xy

d xz

d yz

Note: For a d9 ion in octahedral field, the splitting diagram is an inversion of that
for the octahedral d1 ion (d9 configuration contains one hole)
=> the ground state is 2Eg

4-67

Orgel Diagram for d1, d4, d6 and d9 ions

The relative splitting of the d-orbital energy is

qualitatively identical for octahedral
complexes with d1 or d6 electron configuration
and for d4 or d9 tetrahedral complexes

Similarly, the splitting for d1, d6 tetrahedral

complexes is the same as for d4 and d9
octahedral complexes
Note: the magnitude of splitting is always
smaller for the tetrahedral geometry:
tet = 4/9 oct

Only one electronic transition is possible from a ground state to the excited state:
Eg T2g: octahedral d1 and d6 ion

T2 E:

tetrahedral d1 and d6 ion

T2g Eg: octahedral d4 and d9 ion

E T2:

tetrahedral d4 and d9 ion

4-68

Orgel Diagram for d2, d3, d7 and d8 ions

There are two terms arising from a d2 ion:
3F (ground state) and 3P (excited state)
3P state does not split in Oh
(T2g symmetry)
3F splits into T1g, T2g, and A2g

18 Dq

8 Dq
10 Dq

Non-crossing rule:
states of same symmetry are not allowed
to cross > bending

Note: all transitions from the ground state

are allowed > three absorption bands

4-69

Problem 4-15: a) Assign the absorption bands in the electronic spectra of (a)
[Ni(H2O)6]2+ and (b) [Ni(NH3)6]2+ to the corresponding transitions in the Orgel
diagram on previous page.

b) Estimate the splitting energy oct (=10 Dq) for [Ni(NH3)6]2+ based on above
spectrum

4-70

More Advanced Term Splitting Diagrams...

free ion

ligand field

d-d interaction

4-71

Tanabe Sugano Diagram

More advanced treatment of the energies of

electronic states

The energy of the ground state is taken zero for

all field strengths, an dthe energy of all other
terms are plotted with respect to the ground
state energy

The energy and field strength are expressed in

terms of the Racah parameter B.

Tanabe-sugano diagram for the d2

configuration in an octahedral field

4-72

Problem 4-16: An aqueous solution of [V(H2O)6]3+ shows absorptions at 17200

and 25600 cm1.
a) Assign the absorption band to the corresponding transitions using the TanabeSugano diagram on previous page.

b) Estimate the values for the Racah parameter B and the splitting energy oct.

4-73

Electronic Spectra for d5 Complexes: Mn(H2O)62+

Mn(II) has a d5 high spin electron configuration >

none of the possible (d-d) transitions is spin allowed,
since for any transition the spin of the electron must be
reversed (both higher energy eg orbitals contain
already one electron, according to the Pauli principle
the spin of the second electron must be reversed)
Therefore: all possible transitions are very weak, and
Mn(H2O)62+ is very pale in color

4-74

Nephelauxetic Effect

There is evidence for sharing electrons between metal and ligands

Pairing energies are lower in complexes than in gaseous Mn+ ions,
indicating less interelectronic repulsion
> effective size of the metal orbital has increased

Nephelauxetic = cloud expanding

metal ion

ligands

Co(III)
Rh(III)
Co(II)
Fe(III)
Cr(III)
Ni(II)
Mn(II)

0.35
0.28
0.24
0.24
0.21
0.12
0.07

6 Br
6 Cl
6 [CN]
3 en
6 NH3
6 H2O
6 F

2.3
2.0
2.0
1.5
1.4
1.0
0.8

B0 B
hligands kmetal ion
B0

4-75

Problem 4-17: Using the data in the table on previous page, estimate the
reduction in the interelectronic repulsion in going from the gaseous Fe3+ ion to
[FeF6]3.

4-76

Thermodynamic Aspects of the LFSE

The ligand field stabilization energy has important consequences for the
thermodynamic properties of the transition metal complexes

LFSE as a function of d-electron configuration

Lattice energies for MCl2

Hydration enthalpies of M2+ and M3+

4-77

Irving-Williams Series

The stability for many transition metal complexes follows the following
order:
Mn(II) < Fe(II) < Co(II) < Ni(II) < Cu(II) > Zn(II)

Based on the increasing electron affinity (increasing effective nuclear

charge!) an increase of log K (or H) would be naturally expected
But: The complex stability is also influenced by d-electron-electron
repulsion
> complexes with greater ligand field stabilization energy are expected to
be thermodynamically more stable
> therefore, copper(II) is expected to form the most stable (high-spin)
complexes

4-78

Effect of LFSE
[M(OH2)6]2+ + 3 en

[M(en)3]2+ + 6 H2O

Mn2+

Fe2+

Co2+

Ni2+

Cu2+

Zn2+

log 3

5.6

9.7

13.9

18.4

20.0

12.9

46

67

93

120

105

87

LFSE

4.8

19

44

The overall complex stability parallels the ligand field stabilization energy
contribution and is greatest for Cu(II)