CHEM 1311A Syllabus

• Transition metals and Coordination Chemistry

– Introduction to coordination compounds; stereochemistry,
isomerism and nomenclature
– Coordination compounds: bonding models and energetics
– Coordination compounds: equilibria and substitution reactions
• Bioinorganic chemistry
Fourth Exam – Friday, April 17
 What do these have in common?
• Hemoglobin • “Blue blood”
• Myoglobin • Ferredoxins
• Automobile paints • Rubies
• Anti-cancer drugs (some) • Emeralds
• Industrial catalysts (many) • Legumes (nitrogen fixers)
• Arthritis drugs • Radiopharmaceuticals (some)
• Vitamin B12 • MRI contrast agents
• Cytochromes

All contain a transition metal!!

All are coordination compounds
Many are colored
 Transition metal complex (coordination
compound) terminology
• Coordination compound, coordination complex, complex - a
compound containing a metal ion and appended groups, which are
Lewis bases and may be monatomic or polyatomic, neutral or
anionic.
• Ligand - Lewis base bonded (coordinated) to a metal ion in a
coordination complex.
– Those with only one point of attachment are monodentate
ligands.
– Ligands that can be bonded to the metal through more than one
donor atom are termed bidentate (two points of attachment),
tridentate, etc. Such ligands are termed chelating ligands.
Some examples of ligands (with abbreviations)
I- Br- Cl- F- OH- H2O SCN- NH3 NO2- PR3 P(OR)3 C2H4 PF3 CO CN-

H2N NH2
N N
dien
H
N N NH2 NH2
bipy H2N NH2 H2N
S tren
NH2 PR2
R = Ph, diphos
en R = Me, dmpe NH2
HN N N
NH2 PR2
trien O- -
O
SCH3
O HN NH2
- acac salen
SCH3
O H H
N N
O O-
- EDTA
C O2C CO2-
ox N N N N
C - -
O O O2C CO2- H H
cyclam
 Transition metal complex (coordination
compound) terminology
• Coordination number - number of ligands coordinated to a metal ion,
2-12.
• Coordination geometry or stereochemistry (octahedral, tetrahedral,
square planar) - geometrical arrangements of ligands (donor groups)
about a metal ion.
 Examples of coordination complexes

PPh3 PPh3
Cl PEt3
Ni Ni Ni
Br PPh3 Cl PPh3 Et3P Cl
Br Cl
 Comparison of space filling models of
triphenylphosphine, P(C6H5)3 = PPh3, and
triethylphosphine, P(CH2CH3)3 = PEt3

Space filling models depict Van der Waals radii for atoms and reflect
the effect volume that they occupy
Effect of coordination number and geometry
on absorption spectrum

Comparison of electronic absorption

spectra for [Co(OH2)6]2+ (octahedral)
and [CoCl4]2- (tetrahedral)
 Examples of coordination complexes

H2N
OH2 2+ H2N 2+ H2 3+
H2
H2O OH2 N NH2 N NH2
Ni Ni Co
H2O OH2 N NH2 N NH2
OH2 H2 H N H2 H N
2
2
Effect of ligand on absorption
spectra (and color)
Formulas/structures of some Pt(II) complexes

Composition No. ions Today’s formulation

PtCl2·4NH3 3 [Pt(NH3)4]Cl2

PtCl2·3NH3 2 [Pt(NH3)3Cl]Cl

PtCl2·2NH3 0 cis-[Pt(NH3)2Cl2]
trans-[Pt(NH3)2Cl2]

PtCl2·NH3·KCl 2 K[Pt(NH3)Cl3]

PtCl2·2KCl 3 K2[PtCl4]
 Transition metal complex (coordination
compound) terminology
• Isomers
– Constitutional (structural) isomer - one of two or more
compounds having the same composition but differing in their
atom connectivities.
– Stereoisomer - one of two or more compounds having the same
atom connectivities but different spatial arrangements of atoms.
• Diastereoisomer – stereoisomers not related by mirror
images
• Enantiomer - one of a pair of species that are non-
superimposable mirror images.
 Types of Isomerism
Constitutional
Stereo
(structural)

Diastereomers
Linkage
(geometric)

Enantiomers
Ionization
(optical)

Hydration

● Constitutional (structural) isomers – same composition, different

atom connectivities
● Stereoisomers – same composition, same atom connectivities,
different spatial arrangements
 Stereoisomers: Diastereoisomers

• Compounds that have the same atom connectivities, but which

are not mirror images are diastereoisomers.

X L X
M cis
M L X
L
X
L
L X
M trans
X L

tetrahedral square planar

 Examples of coordination complexes

PPh3 PPh3
Cl PEt3
Ni Ni Ni
Br PPh3 Cl PPh3 Et3P Cl
Br Cl
 Stereoisomers: Diastereoisomers

• Compounds that have the same atom connectivities, but which

are not mirror images are diastereoisomers.

L L
L X
ML4X2 L
M
X
M
L X cis
L X
L L

X X
L L L L
M M trans
L L L L
X X

L L
L X L X
M M trans
X L X L
L L
 Examples of coordination complexes

H2N 1+ Cl H2N
H2 H2 1+ H2 3+
Cl NH2 N N N NH2
Co Co Co
Cl NH2 N NH2
N N H2 H N
H2N H2 Cl H2 2
 Stereoisomers: Diastereoisomers

• Compounds that have the same atom connectivities, but which

are not mirror images are diastereoisomers.

ML3X3 X X
L L L L
M M mer
L X L X
X X

X X
L X L X
M M fac
L X L X
L L
Stereoisomers: Enantiomers (optical isomers)

• Compounds that have no center or plane of symmetry exist in

non-superimposable, mirror-image forms.

F F

Br C C Br
Cl Cl
H H
Optical rotation
 Stereoisomers: Enantiomers

• Compounds that have no center or plane of symmetry exist in

non-superimposable, mirror-image forms.

Rotate by 180E

F F

Br C C Br
Cl Cl
H H
 Stereoisomers: Enantiomers

• Compounds that have no center or plane of symmetry exist in

non-superimposable, mirror-image forms.

H2N
H2 3+
N NH2
Co
N NH2
H2 H N
2
 Stereoisomers: Enantiomers

• Compounds that have no center or plane of symmetry exist in

non-superimposable, mirror-image forms.
– Even MA2B2C2 can exist in enantiomeric forms (optical
isomers)

Rotate 180o about

A A A-M-B axis
A C C
B C
A
M M
B C C
A C
B
B B
How many diastereoisomers can exist for the complex ion
[Co(H2NCH2CH2NH2)(NH3)2Cl2]+ ?

How many of these diastereoisomers have nonsuperimposable mirror

image forms?
 How many diastereoisomers can exist for [Co(dien)(Cl)(NO2)2]?

H
H2N NH2 N N
dien = = = N N
NH
NH2 H2N
How many stereoisomers (diastereoisomers and enantiomeric forms)
can exist for [Co(H2NCH2CH2O)3]?
The tetradentate ligand shown below forms six-coordinate complexes
with Co(III) having the composition [CoLX2]+ where X is a mondentate
ligand. How many diastereoisomers can be formed?

HN NH2 N N

=
HN NH2 N N
Energy changes for formation of ML6n+
n+ n+ n+
M +6L ML6 ML 6
(octahedral)

E
d z 2 d x2 - y 2

)E
e-e replusion d xz dxy dyz
differential replusions
of d orbitals
electrostatic
attraction
 Magnetic properties depend upon the
magnitude of Δo

• High spin – maximum number of unpaired electrons for dn

– Spin pairing energy is greater than ΔE (Δo)
• Low spin – minimum number of unpaired electrons for dn
– Spin pairing energy is less than ΔE (Δo)
 Dependence of magnetic and spectral
properties on ligand type

I– < Br– < SCN– < Cl– < NO2– < F– < OH– < C2O42– ≈ H2O < NCS–
< py < NH3 < en < bipy < phen < NO2– < PR3 < CN– ≈ H– < CO
Weak Field Strong Field
Small Δ Large Δ
Frequently high spin Frequently low spin
Poor σ Donors Strong σ Donors
π Bases (donors) π Acids (acceptors)
 Constructing an energy level diagram for a
complex with F donor ligands

F*

np F*

ns eg *
F*

)
t2g
(n-1) d n

L orbitals

F
y z z F
F
x x y

x
 Energy level diagram for complex
with F donor ligands

F*

np
F*

ns eg*
F*
)
t2g
(n-1) d n

L orbitals

F
F
F
Metal-ligand B-bonding interactions

dB-pB donor interactions; halide, hydroxide

dB-pB acceptor interactions (rare)

dB-dB acceptor interactions; phosphorus, arsenic

dB-B* acceptor interactions; CO, CN-, NO, RNC

dB-B* acceptor interactions; olefins (C=C)

 Energy level diagram for complex
with F and B donor ligands

F*

np
F*

ns eg* t2g
y z z
F*
x x y ) t
2g
B*
x (n-1) d

n L orbitals
B
F
F
F
 HOMO and LUMO for cyanide ion

E p

s
 Energy level diagram for complex
with F and B acceptor ligands

F*

np
F*
B*
n L pi acceptor
ns eg* orbitals
F*

)
(n-1) d t2g
B

L orbitals

F
F
F
 Energy level diagrams for complexes with F
only, F plus B donor, and F plus B acceptor
ligands

np

L pi acceptor
ns orbitals

)
)
)
(n-1) d

L orbitals
 Effect of B-donor and B-acceptor interactions
on ) in octahedral complexes

eg* eg* eg*

)
) t2g*
)
t2g
t2g

energy of d-orbitals F bonding only F + B donor F + B acceptor

prior to interaction
with ligands
intermediate weak field strong field
field ligands ligands ligands
 Dependence of magnetic properties on L
I– < Br– < SCN– < Cl– < NO2– < F– < OH– < C2O42– ≈ H2O < NCS–
< py < NH3 < en < bipy < phen < NO2– < PR3 < CN– ≈ H– < CO
Weak Field Strong Field
Poor σ Donors Strong σ Donors
π Bases (donors) π Acids (acceptors)
● All 4d and 5d transition metal complexes are low spin.
● All CN– and CO complexes are low spin.
● All aqua ions of 3d metals are high spin.
● d4 Cr2+, Mn3+ High spin except for very strong field ligands.
● d5 Mn2+ Almost always high spin, t2g3eg2.
Fe3+ Low spin for bpy or stronger field ligands.
● d6 Fe2+ High spin for NH3 and weaker field ligands
Low spin for bpy and stronger field ligands.
Co3+ Low spin for NH3 and stronger field ligands.
● d7 Co2+ Usually high spin.
Variation of M-O distance in [M(OH2)6]3+ with
number of M d-electrons

2.04
Ti
2.02 Mn(III),Fe(III) are h.s.
2.00 V Mn Fe Co(III) is l.s.
M-O distance/Ǻ

1.98

1.96
Cr
1.94

1.92

1.90

1.88
Co
1.86
0 1 2 3 4 5 6 7

No. of d electrons

Data are for {[Cs(OH2)6][M(OH2)6]}(SO4)2 J.

Chem. Soc., Dalton Trans. 1981, 2105
 Electronic absorption spectra
• Selection rules
– Electronic transitions that occur without change in number
of unpaired electrons (spin multiplicity) are allowed
– Electronic transitions that involve a change in the number
of unpaired spins are “forbidden” and are therefore of low
intensity.
> e.g., solutions of high-spin d5, e.g., Mn(II), complexes
are lightly colored
Allowed vs forbidden transitions

dx2-y2 dz2 dx2-y2 dz2

E dxz dxy dyz dxz dxy dyz

dx2-y2 dz2 dx2-y2 dz2

dxz dxy dyz dxz dxy dyz

Number of d electrons and spectral intensity

[Mn(OH2)6]2+
 Electronic absorption spectra

– Electronic transitions are symmetry forbidden in

complexes with a center of symmetry (octahedral), but are
not symmetry forbidden in complexes without a center of
symmetry (tetrahedral)

Comparison of electronic absorption

Comparison of electronic absorption
spectral intensities for [Mn(OH2)6]2+
spectral intensities for [Co(OH2)6]2+
and [MnBr4]2- (symmetry)
and [CoCl4]2- (symmetry)
 Electronic absorption spectra, cont’d
• Absorption bands are broad because metal-ligand bonds are
constantly changing distance (vibration) and since electronic
transitions occur faster than atomic motions this means that
there are effectively many values of Δo.
• d0 and d10 complexes do not have d-d transitions and are
colorless unless there are other types of absorptions with
energies that fall in the visible region

Ph
Base
Ph

N N
N N
Ph Zn Ph + Base Ph Zn Ph
N N N N

Ph
Ph

• d1 and d9, and high-spin d4 and d6 ions have only one spin-
allowed transition; high-spin d2, d3, d7 and d8 have three spin-
allowed transitions
 Transitions in d1 and d2 complexes

dx2-y2 dz2

dxz dxy dyz

dx2-y2 dz2 dx2-y2 dz2

dxy1 dx2-y21 dxz1dz21 dyz1dz21
dx2-y2 dz2
E
dxz dxy dyz dxz dxy dyz dxz1 dx2-y21 dxy1dz21 dyz1dx2-y21
dxz dxy dyz

dx2-y2 dz2 dx2-y2 dz2

dxz dxy dyz dxz dxy dyz

 Some compounds are very highly colored
because of charge transfer transitions – even
some with no d electrons
● There can be electronic transitions in the visible region that do
not involved d-electrons
− MnO4- (purple) and CrO42- (yellow) are intensely colored
because electrons in filled oxygen based orbitals are
excited into empty d-orbitals (LMCT)
− Ligand to Metal Charge Transfer (LMCT) bands have few
selection rule restrictions and are typically very intense
● Metal to Ligand Charge Transfer (MLCT) bands may also occur
for complexes with d-electrons.
− There are few selection rules and the high intensity of these
bands may mask d-d transitions.
Crystal field splitting in tetrahedral complexes
• Tetrahedral arrangement of four ligands
showing their orientation relative to the
Cartesian axes and the dyz orbital.
• The orientation with respect to dxz, dxz and
dxy is identical and the interaction with
these orbitals is considerably greater than
with the dz2 and dx2- y2 orbitals; therefore
the dyz, dxz and dxy orbitals are higher in
energy than dz2 and dx2- y2 .
• Because there are only four ligands and
the ligand electron pairs do not point
directly at the orbitals, Δt ~4/9 Δo. As a
result the spin-pairing energy is always
greater than Δ and tetrahedral complexes
are always high spin.
Comparison of crystal field splittings for
octahedral, square planar and tetrahedral
ligand fields
Factors affecting the magnitude of ) (Crystal
Field Splitting)
● Charge on the metal. For first row transition elements )O
varies from about 7,500 cm-1 to 12,500 cm-1 for divalent ions
and 14,000 cm-1 to 25,000 cm-1 for trivalent ions.
● Position in a group. )O values for analogous complexes of
metal ions in a group increase by 25% to 50% on going from
one transition series to the next. This is illustrated by the
complexes [M(NH3)6]3+ where ) values are 23,000 cm-1 for
M=Co; 34,000 cm-1 for M=Rh and 41,000 cm-1 for M=Ir.

Smaller M–L distances in more Larger 4d and 5d orbitals

highly charged ions leads to overlap and interact more strongly
stronger interaction with L making with L making the eg orbitals
the eg orbitals more antibonding more antibonding and
and increasing )O. increasing )O.
 Factors affecting the magnitude of ) (Crystal
Field Splitting)
● Identity of the ligand. The magnitude of ΔO reflects the extent and
way in which the metal interacts with the ligands.
− Better σ-donor Lewis base ligands are higher in the
spectrochemical series because the eg orbitals are more
antibonding and destabilized.
− Better π-donor ligands are lower in the spectrochemical series
because the t2g orbitals are more destabilized since they are
now π-antibonding.
− Better π-acceptor ligands are higher in the spectrochemical series
because the t2g orbitals are more stabilized since they are now
π-bonding.

I– < Br– < SCN– < Cl– < NO2– < F– < OH– < C2O42– ≈ H2O < NCS–
< py < NH3 < en < bipy < phen < NO2– < PR3 < CN– ≈ H– < CO
Weak Field Strong Field
Poor σ Donors Strong σ Donors
π Bases (donors) π Acids (acceptors)
Variation of )O in octahedral Ti(III) complexes
Ti(III) is a d1 ion and exhibits one absorption in the electronic
spectrum of its metal complexes due to transition of the electron
from the t2g (lower energy) orbitals to the eg (higher energy)
orbitals. The energy of the absorption corresponds to )O.

Ligand )O/cm-1*
Br- 11,400
Cl- 13,000
(H2N)2C=O 17,550
NCS- 18,400
F- 18,900
H 2O 20,100
CN- 22,300
*E = h< = hc/8
Factors affecting the magnitude of ) (Crystal
Field Splitting)
● Geometry and coordination number. For similar ligands )t
will be about 4/9 )O. This is a result of the reduced number of
ligands and their orientation relative to the d orbitals. Recall that
the energy ordering of the orbitals is reversed in tetrahedral
complexes relative to that in the octahedral case.
 Thermodynamic vs kinetic stability

• Stability in a thermodynamic sense refers to the energetics of a

formation or decomposition reaction )G = )H - T)S
• Stability in a reactivity sense refers to the rate with which a
given reaction occurs )G‡ = )H‡ - T)S‡
• Complexes that undergo substitution with half-lives less than
about one minute are referred to as labile; those that are less
reactive are termed inert.
• Complex stability and reactivity do not necessarily correlate with
ligand field strength; the latter refers to spectroscopic and
magnetic properties.
• Thermodynamic and kinetic stabilities sometimes parallel but
often they do not.
– [Ni(CN)4]2& illustrates the latter case; the overall equilibrium
constant its formation is >1030 but the second order rate
constant for CN& exchange is >5 x 105 M-1 s-1
 Ligand Substitution Energetics

ΔG‡

M–X + Y
ΔGº

M–Y + X

The nature of the M–X and M–Y bonding interactions determine ΔGº and
ΔG‡.
•ΔGº is a function of the relative strengths of M–X vs. M–Y.
•ΔG‡ is a function of the lability of the M–X bond.

Thermodynamic and kinetic stabilities sometimes parallel but often they

do not.
 Stepwise formation of [Cu(NH3)4]2+

[Cu(OH2)4]2+ + NH3 W [Cu(OH2)3(NH3)]2+ + H2O log K1 = 4.22

[Cu(OH2)3(NH3)]2+ + NH3 W [Cu(OH2)2(NH3)2]2+ + H2O log K2 = 3.50
[Cu(OH2)2(NH3)2]2+ + NH3 W [Cu(OH2)(NH3)3]2+ + H2O log K3 = 2.92
[Cu(OH2)(NH3)3]2+ + NH3 W [Cu(NH3)4]2+ + H2O log K4 = 2.18

[Cu(NH ) 2+ ]
[Cu(OH2)4]2+ + 4 NH3 W [Cu(NH3)4]2+ + 4 H2O β = 34
4 [Cu2+ ][NH ]4
3
Speciation is determined by ligand concentration
[Cu(OH2)4]2+ + n NH3 = [Cu(OH2)4-n(NH3)n]2+
1.0
0.9
0.8
n=0 n=4
0.7
0.6
Fraction

n=1 n=3
n=2
0.5
0.4
0.3
0.2
0.1
0.0
6 4 2 0
-log[NH3]
 Chelating ligands have larger formation constants
than comparable non-chelating ligands; the Chelate
Effect is largely (substantially?) entropic in origin

[Cu(OH2)4]2+ + en W [Cu(OH2)2(en)]2+ + 2 H2O log K1 = 10.6

)H = -54 kJ mol-1, )S = 23 J K-1 mol-1

[Cu(OH2)4]2+ + 2 NH3 W [Cu(OH2)2(NH3)2]2+ + 2H2O log K2 = 7.7

)H = -46 kJ mol-1, )S = -8.4 J K-1 mol -1
Ligand substitution in coordination complexes
● Arguably the most important reaction of coordination complexes
is ligand substitution.
● There are two limiting mechanisms for substitution reactions
– associative parallels the SN2 reaction in organic chemistry;
the reaction involves an intermediate of higher
coordination number. rate = k[complex][L]

> associative reactions are more important for larger metal

ions and for those that have vacancies in the t2g orbitals
Ligand substitution in coordination complexes
● There are two limiting mechanisms for substitution reactions
– associative (already discussed)
– dissociative parallels the SN1 reaction in organic chemistry;
the reaction involves an intermediate of lower
coordination number. rate = k[complex]

● The simplest substitution is ligand exchange which is not

complicated by thermodynamics since ΔG = 0.
– exchange rates of water have been most extensively studied
– rate constants for water exchange range from 1.1x10-10 s-1 to
5x109 s-1
 Observations on water exchange

● An increase in oxidation state for the metal reduces the rate of

exchange
● Early (larger) elements in a period tend to have a greater
contribution from associative processes
● Heavier (larger) elements in a family have a greater contribution
from associative processes; also greater bond strengths
decrease rate of dissociative processes
● Occupancy of (antibonding) eg orbitals increases the rate for all
oxidation states
Water exchange rates in aquo metal ions
Rate constantsa for water exchange
[MLn(OH2)]n+ k/s-1-1 [MLn(OH2)]n+ k/s-1-1
[Ti(OH2) 6]3+ 1.8 x 105
[V(OH2)6] 2+ 8.7 x 101 [V(OH2)6] 3+ 5.0 x 102
[Cr(OH2)6] 2+ >108 [Cr(OH2)6] 3+ 2.4 x 10-6
[Mn(OH2)6] 2+ 2.1 x 107
[Fe(OH2)6]2+ 4.4 x 106 [Fe(OH2)6]3+ 1.2 x 102
[Ru(OH2)6]2+ 1.8 x 10-2 [Ru(OH2)6]3+ 3.5 x 10-6
[Co(OH2)6]2+ 3.2 x 106
[Ni(OH2)6] 2+ 3.2 x 104
[Pd(OH2) 4]2+ 5.6 x 10-2
[Pt(OH2)4]2+ 3.9 x 10-4
[Cu(OH2)6]2+ >107
[Zn(OH2)6]2+ >107
[Cr(NH3)5OH2]3+ 5.2 x 10-5
[Co(NH3) 5OH2]3+ 5.7 x 10-6
[Rh(NH3) 5OH2]3+ 8.4 x 10-6
[Ir(NH3)5OH2]3+ 6.1 x 10-8
aAll
rate constants are expressed as first order rate constants for
comparative purposes even though some reactions are associative.
 Electron transfer reactions: importance of
orbital occupancy and spin state on rate
● Electron transfer is second only to substitution in importance as a
characteristic reaction of coordination complexes and especially in
biological systems.
● Again the simplest reaction is outer-sphere electron exchange where
)G=0
● Rates of electron exchange vary enormously across the transition series,
but two things are invariably true:
– The rate of electron transfer is greatest when electrons are transferred
from a t2g orbital on the reductant to a t2g orbital on the oxidant.
– Changes in bond distance in either oxidant or reductant upon electron
transfer are minimal in these cases.
– However, when electrons are lost/gained from
Complex
eg orbitals reaction rates-1 -1
e- config M-L BD, D k , M s ex
decrease and bond distance changes increase.
[Co(NH3)6]2+ t2g5eg2 2.114 8 x 10-6
[Co(NH3)6]3+ t2g6 1.936
[Ru(NH3)6]2+ t2g6 2.144 8.2 x 102
[Ru(NH3)6]3+ t2g5 2.104
Electron transfer reactions: importance of
orbital occupancy and spin state on rate
Complex e- config M-L BD, kex, M-1
D s-1
[Co(NH3)6]2+ t2g5eg2 2.114
8 x 10-6
[Co(NH3)6]3+ t2g6 1.936
[Cr(OH2)6]2+ t2g3eg1 2.106
≤10-5
[Cr(OH2)6]3+ t2g 3 1.959
[Mn(CN)6]4- t2g5 1.95
[Mn(CN)6]3- t2g4 1.976
[Fe(CN)6]4- * t2g6 1.900
6
[Fe(CN)6 ]3- * t2g 5 1.926
[Ru(NH3)6]2+ t2g6 2.144
8.2 x 102
[Ru(NH3)6]3+ t2g5 2.104

*νCN = 2121 cm-1 for Fe(III), 2021 cm-1 for Fe(II)