Transition Metal

UNIT 5: COORDINATION CHEMISTRY AND

TRANSITION ELEMENTS

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CONTENT
2

Coordination Numbers and Geometries

Types of Ligands
Isomerism
Nomenclature
Stability of Coordination Compounds
Reactivity and Reaction Mechanisms of Coordination
Compounds
Ligand Field Theory and Ligand Field Splittings and Spectra
Crystal Field Approach
Magnetic Properties of Transition Metal Compounds
Chemistry of the first row transition elements

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Coordination Compounds
Nature of coordination compounds is3 determined by both the oxidation

number of the central ion and its coordination number.

The coordination number is (mostly) constant for a metal with a given

oxidation number.
First coordination sphere: central metal ion and its ligands

First Coordination Sphere

Coordination number is often 2 x oxidation number (many exceptions)
Mostly predictable geometry:

Coordination number = 2, linear

Coordination number = 4, square planar or tetrahedral
Coordination number = 6, octahedral
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Coordination Compound
4

Consist of a complex ion and necessary counter ions

[Co(NH3)5Cl]Cl2

We can see it has a coordination no. of 6.

Complex ion: [Co(NH3)5Cl]2+
Co3+
=
=

+ 5 NH3 + Cl-

1(3+) + 5 (0)
2+

Counter ions:
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2 Cl-

+ 1(1-)

Complex Ion
5

Species where transition metal ion is surrounded by

a certain number of ligands.

Transition metal ion:

Ligands:

Lewis acid
Lewis bases

Co(NH3)63+
Pt(NH3)3Br+

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Ligands
7

Molecule or ion having a lone electron pair that can

be used to form a bond to a metal ion (Lewis base).

coordinate covalent bond: metal-ligand bond

monodentate:
bidentate:
polydentate:

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one bond to metal ion

two bond to metal ion
more than two bonds to a
metal ion possible

Formulas of Coordination Compounds

8

1.

Cation then anion

2. Total charges must balance to zero
3. Complex ion in brackets
K2[Co(NH3)2Cl4]
[Co(NH3)4Cl2]Cl

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NOMENCLATURE
9

1.
2.
3.
4.
5.
6.
7.

In naming salts, the cation is written before the anion

Within a complex ion , the ligands are named before
the metal ion
Ligands are listed in alphabetical order
Prefixes that give the number of ligands are not
considered in determining the alphabetical order
The names of anionic ligands end in the letter o
Neutral ligands generally have the molecule name.
Exception are water and ammonia
A greek prefix (di,tri,tetra, penta, and hexa) is used to
indicate the
number of each ligand.

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NOMENCLATURE
10

8.

If the complex is an anion, its name ends in -ate

9.

The oxidation number of the metal is given in

parentheses

10. Some metals which are part of the anion complex will

use the latin name with -ate as an ending

11. When the name of the ligand has a prefix, use: bis(2),

tris (3), tetrakis (4) to give the number of ligands in the

compound.
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Names of Coordination Compounds

11

1.

Cation then anion

2. Ligands

in alphabetical order before metal ion

neutral:
molecule name*

anionic:
-ide -o

prefix indicates number of each

3. Oxidation state of metal ion in () only if more than
one possible
4.

If complex ion = anion, metal ending -ate

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Cation Name Latin Name

Copper
Gold
Iron
Lead
Silver
Tin

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Cuprum
Aurum
Ferrum
Plumbum
Argentum
Stannum

Anion Name
Cuprate
Aurate
Ferrate
Plumbate
Argentate
Stannate

13

Anion Name
Ligand Name
Bromide, BrBromo
Carbonate, CO32- Carbonato
Chloride, ClChloro
Cyanide, CNCyano
Fluoride, F- Fluoro
Hydroxide, OH- Hydroxo
Oxalate, C2O42Oxalato
Oxide, O2- Oxo
Sulfate, SO42Sulfato
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Molecule
Ammonia, NH3

Ligand Name
Ammine

Carbon monoxide,CO
Water
Ethylenediammine, en

Carbonyl
Aqua
Ethylenediammine

EXAMPLES:
[Co(NH3)5Cl]Cl2 Pentaamminechlorocobalt(III)
Chloride
K4[Fe(CN)6]
Potassium Hexacyanoferrate(II)
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Examples
15

K2[Co(NH3)2Cl4]

potassium diamminetetrachlorocobaltate(II)

[Co(NH3)4Cl2]Cl

tetraamminedichlorocobalt(III) chloride

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16

20_441

Isomers
(same formula but different properties)

Stereoisomers
(same bonds, different
spatial arrangements)

Structural
isomers
(different bonds)

Coordination
isomerism

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Geometric
(cis-trans)
isomerism

Linkage
isomerism

17

Optical
isomerism

Structural Isomerism 1
18

Coordination isomerism:

Composition of the complex ion varies.

[Cr(NH3)5SO4]Br

and [Cr(NH3)5Br]SO4

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Structural Isomerism 2
Ligand isomerism:

19

Same complex ion structure but point of

attachment of at least one of the ligands differs.

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[Co(NH3)4(NO2)Cl]Cl
and [Co(NH3)4(ONO)Cl]Cl

Linkage Isomers
20

[Co(NH3)5(NO2)]Cl2

[Co(NH3)5(ONO)]Cl2

Pentaamminenitrocobalt(III)
chloride

Pentaamminenitritocobalt(III)
chloride

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Stereoisomerism 1
21

Geometric isomerism (cis-trans):

Atoms or groups arranged differently spatially

relative to metal ion

Pt(NH3)2Cl2

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22

20_444

H3N

Cl

H3N

NH3
H3N

NH3

Cl
NH3

Cl

Cl

Cl

Co

Co
Cl

Cl
(a)
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NH3

Co

Co
H3N

Cl

23

(b)

Stereoisomerism 2

Optical isomerism:
20_446

24

Have opposite effects on plane-polarized light

(no superimposable mirror images)
Polarizing
filter
Tube
containing
sample

Unpolarized
light

Polarized
light
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Rotated
polarized light

20_448

Mirror image
of right hand
Left hand

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Right hand

25

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26

20_449

N
N
N

N
N
N

Co

Co

Mirror image
of Isomer I

N
N

N
Isomer I

Isomer II

N
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Co

N
27

N
N

20_450

Cl
N
N

Co

Cl
trans

N
N

Co
Cl

(a)

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The trans isomer and

its mirror image are
identical. They are not
isomers of each other.

Cl
N
N
Cl

Cl
N
N

cis

N
N

Co

Co

Cl

Isomer II cannot be
superimposed exactly
on isomer I. They are
not identical structures.
Cl

N
Cl
N

N
N

Co

N
Cl

Isomer I N

Isomer II N

(b)

Isomer II has the same

structure as the mirror
image of isomer I.

28

BONDING IN TRANSTION
METALS
29

VALENCE BOND THEORY OR

HYBRIDISATION

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Valence Bond Theory

30

Uses hybrid orbitals to hold the donated electron

pairs for formation of the coordinate

covalent bonds
Can explain the structure and magnetic properties.
Select low energy empty metal orbitals to hybridize
for the appropriate geometry
If there are not enough orbitals, pair up any
unpaired metal electrons to free up orbitals.

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31

Hybrid orbital sets:

d2sp3 octahedral
sp3 tetrahedral
dsp2 square planar

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[FeF6 ]334

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35

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37

GROUP WORK
38

Write box diagrams for the electron configuration of

Cr(III), using high spin and low

spin arrangements of 6 ligands.
Would there be two arrangements for Cr(III)?
Consider the electron configurations for Co
Co [Ar]3d74s2
What is the valence bond description of Co(NH3)63+?

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Valence Bond Theory Limitations

39

Valence bond theory limitations:

1. Explains, but does not predict.
2. Qualitative explanations; does not explain relative
stability.
3. Cannot explain color and spectra.
4. Cannot explain relative stability of structural
isomers.

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Introduction to Crystal Field theory

40

Assumes that the only interaction between the metal

ion and the ligands, is an electrostatic or ionic one.

with the ligands being regarded as negative point
charges.
Though we know this is not entirely the case, the
theory does provide some interpretation of the
properties of these complexes.

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Crystal Field Effects

41
In an isolated metal ion
the five d-orbitals are

degenerate, ie they are at the same energy level.

If they are exposed to a symmetric field of
negative charges they will remain degenerate but
the energy level would be higher due to repulsion
between the negative ligand field and the
negative electrons in the d-orbitals.
If the field which the d-orbitals are exposed to
are from real ligands, such as H2O, as in the case
of [Fe(H2O)6]3+, the symmetry of the field will not
be spherical and the degeneracy of the d-orbitals
will be removed.
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Octahedral symmetry
42

ENERGY

eg

Metal ion in a
symmetric
ligand field

Free metal ion

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Splitting of the
five d-orbitals
by an octahedral
ligand field

t2g

43

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Splitting of the d orbitals

44

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Colour and the Spectrochemical Series

45

important aspects of CFT is that not all ligands

are identical when it comes to causing a

separation of the d-orbitals.
There is clear evidence for this from the
multitude of colours available for a given metal
ion when the ligands or stereochemistry are
varied.
For octahedral complexes this is a reflection of
the energy difference between the higher dz2, dx2y2 (eg subset) and the dxy, dyz, dxz (t2g subset).
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46

In general the difference in energy between the two

sets of degenerate orbitals is denoted by .

This corresponds to wavelengths of light in the
visible spectrum and the colour of complexes can be
attributed to electronic transitions between the lower
and higher energy sets of d-orbitals.
In other words complexes are coloured because the
magnitude of corresponds to the energies in the
visible region of the electromagnetic specrum.

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SPECTROCHEMICAL SERIES
47

The SPECTROCHEMICAL SERIES is a list of

ligands ranked in order of their ability to cause large

orbital separations.
When metal ions that have between 4 and 7 electrons
in the d orbitals form octahedral compounds, two
possible electron distributions can occur. These are
referred to as either weak field - strong field or
high spin - low spin configurations.

Increasing
I- < Br- < SCN- ~Cl- < F- < OH- ~ ONO- < C2O42- < H2O
< NCS- < EDTA4- < NH3 ~ pyr ~ en < bipy < phen < CN- ~ CO
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High spin
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Low spin
48

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49

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50

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51

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[V(H2O)6]2+

[V(H2O)6]3+

[Cr(NH3)6]3+

[Cr(NH3)5Cl]2+s

52

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53

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54

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55

20_459

Tetrahedral Complexes
56

(a)

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dz 2

dxy
(b)

dx2 y2

dxz

dyz

Take for example, Fe2+- d6

57

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58

A high spin complex may be defined as one in which the d-

orbitals are arranged according to Hunds rule to give the

maximum number of unpaired electrons whereas a low spin
complex may be defined as one in which the d electrons are
paired to give the maximum number of doubly occupied dorbitals and a minimum number of unpaired electrons.
The terms weak field, strong field give an indication of the
splitting abilities of the ligand.
Water and those ligands to the left such as the halides,
always give rise to small splittings of d orbitals for first row
transition metal ions and hence are referred to as weak field
ligands.
Conversely, CN- is a strong field ligand, since it causes large
splittings of the d-orbitals.
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Magnetic Moments
59

For first row transition metals the magnetic moment

may be predicted, for other rows it becomes more

complex orbital contributions etc.
To predict the magnetic moment, we can use the
simple spin-only formula:

= [4S(S+l)]
Bohr Magneton (BM)
Where S is the spin quantum number (1/2 for each
unpaired electron).
An alternative representation is:

= [n(n+2)]
Bohr Magneton (BM)
Where n is the number of unpaired electrons.

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Examples
60

K2CuCl4
metal ion
number of d

Cu2+

3[Fe(H2O)6] [Co(CN)6]
3+

Fe3+

stereochemistry

tetrahedral

octahedral

High Spin/Low Spin

Not relevant

High Spin

electrons

# of unpaired
electrons
magnetic moment
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[Co(F)6]3-

(3) B.M

(35) B.M.

Co3+

Co3+

octahedral

octahedral

Low spin

High spin

(24) B.M.

Magnetic Moments of Octahedral,

Tetrahedral and Square Planar Complexes
61

Comparison of calculated spin-only magnetic moments with experimental

data for some octahedral complexes
so (B.M.)
obs (B.M.)
Ion
Configuration
d1 (t2g1)
Ti(III)
1.6-1.7
3 = 1.73
d2 (t2g2)
V(III)
2.7-2.9
8 = 2.83
d3 (t2g3)
Cr(III)
3.7-3.9
15 = 3.88
d4 high spin (t2g3 eg1)
Cr(II)
4.7-4.9
24 = 4.90
d4 low spin (t2g4)
Cr(II)
3.2-3.3
8 = 2.83
Mn(II)/ Fe(III) d5 high spin (t2g3 eg2)
5.6-6.1
35 = 5.92
Mn(II)/ Fe(III) d5 low spin (t2g5)
1.8-2.1
3 = 1.73
d6 high spin (t2g4 eg2)
Fe(II)
5.1-5.7
24 = 4.90
d7 high spin (t2g5 eg2)
Co(II)
4.3-5.2
15 = 3.88
d7 low spin (t2g6 eg1)
Co(II)
1.8
3 = 1.73
d8 (t2g6 eg2)
Ni(II)
2.9-3.3
8 = 2.83
d9 (t2g6 eg3)
1.7-2.2
3 = 1.73
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62

Comparison of calculated spin-only magnetic moments with

experimental data for some tetrahedral complexes
Ion

Configuration so(B.M.)

Cr(V)
Cr(IV) /
Mn(II)
Fe(V)

d1 (e1)

3 = 1.73

1.7-1.8

d2 (e2)

8 = 2.83

2.6 - 2.8

d3 (e2 t21)

15 = 3.88

3.6-3.7

Cr(II)

d4 (e2 t22)

24 = 4.90

Mn(II)

d5 (e2 t23)

35 = 5.92

5.9-6.2

Fe(II)

d6 (e3 t23)

24 = 4.90

5.3-5.5

Co(II)

d7 (e4 t23)

15 = 3.88

4.2-4.8

Ni(II)

d8 (e4 t24)

8 = 2.83

3.7-4.0

Cu(II)

d9 (e4 t25)

3 = 1.73

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obs (B.M.)

The Stability of Metal Complexes and the Chelate Effect

63

A metal ion in solution does not exist in isolation, but in

combination with ligands (such as solvent molecules or

simple ions) or chelating groups, giving rise to complex ions
or coordination compounds.
These complexes contain a central atom or ion, often a
transition metal, and a cluster of ions or neutral molecules
surrounding it.
Many complexes are relatively unreactive species remaining
unchanged throughout a sequence of chemical or physical
operations and can often be isolated as stable solids or
liquid compounds. Other complexes have a much more
transient existence and may exist only in solution or be
highly reactive and easily converted to other species.
All metals form complexes, although the extent of formation
and nature of these depend very largely on the electronic
structure of the metal.
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Thermodynamic Stability
64

The "stability of a complex in solution" refers to the

degree of association between the two species involved

in the state of equilibrium. Qualitatively, the greater
the association, the greater the stability of the
compound.
The magnitude of the (stability or formation)
equilibrium
constant
for
the
association,
quantitatively expresses the stability. Thus, if we have
a reaction of the type:
M + 4L ML4
then the larger the stability constant, the higher the
proportion of ML4 that exists in the solution.
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65

A complex is called stable if the equilibrium is on

the side of the products.

Free metal ions rarely exist in solution so M will
usually be surrounded by solvent molecules which
will compete with the ligand molecules, L, and be
successively replaced by them. For example:

[Cu(H2O)6]2+ + :NH3
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[Cu(H2O)5(NH3)]2+ + H2O

66

For simplicity, we generally ignore these solvent molecules and

write stability constants as follows:

l.
M + L ML
K1 = [ML] / [M] [L]
2. ML + L ML2
K2 = [ML2] / [ML] [L]
3. ML2 + L ML3 K3 = [ML3] / [ML2] [L]
4. ML3 + L ML4 K4 = [ML4] / [ML3] [L]
where K1, K2 etc. are referred to as "stepwise stability constants".
Alternatively, we can write the "Overall Stability Constant" thus:
M + 4L ML4
4 = [ML4]/ [M] [L]4
The stepwise and overall stability constants are therefore related

as follows:
b4 =K1.K2.K3.K4 or more generally,
bn =K1.K2.K3.K4--------------K n
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67
If we take as an example,
Cu2+ + NH3 Cu(NH3)2+
K1 = [Cu(NH3)2+]/[Cu2+]
[NH3]
CuNH32+ + NH3 Cu(NH3)22+
K2 = [Cu(NH3)22+]/
[Cu(NH3)2+] [NH3]
etc. where K1, K2 are the stepwise stability constants.
Also:

4 = [Cu(NH3)42+]/[Cu2+] [NH3]4

The addition of the four ammine groups to copper shows a

pattern found for most formation constants, in that the

successive stability constants decrease. In this case, the four
constants are:
logK1 = 4.0; logK2 =3.2; logK3 =2.7; logK4 = 2.0 or log4 =11.9

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Some other equation to Note

68

G = -RTLn

G = -2.303 RTLog10
G = H - TS

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The Chelate Effect

69

Polydentate ligands are called Chelates because

they are able to grasp the metal between two or

more donor atoms. The term chelate was first
applied in 1920 by Sir Gilbert T. Morgan and
H.D.K. Drew [J. Chem. Soc., 1920, 117, 1456], who
stated:
"The adjective chelate, derived from the great claw
or chele (Greek) of the lobster or other
crustaceans, is suggested for the caliper-like groups
which function as two associating units and fasten
to the central atom so as to produce heterocyclic
rings.

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70

In general chelating ligands form more stable

complexes than do related monodentate ligands. The

special stability associated with the formation of
chelates is called the chelate effect. The chelate
effect can be seen by comparing the reaction of a
chelating ligand and a metal ion with the
corresponding reaction involving comparable
monodentate ligands.

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Monodentate vs Bidentate
71

H2C
H2N

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CH2
NH2

NH3

72

It has been known for many years that a

comparison of this type always shows that the

complex resulting from coordination with the
chelating ligand is much more
thermodynamically stable.
This can be seen by looking at the values for adding
two monodentates compared with adding one
bidentate, or adding four monodentates compared
to two bidentates, or adding six monodentates
compared to three bidentates.
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Thermodynamic data of the reaction of ammonia and 1,2diaminoethane (ethylenediamine) with Ni2+
73

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# of ligands

log

G (kJmol-1)

1 NH3

2.8

-16

2 NH3 (1 en)

5.0 (7.51)

-28.5 (-42.8)

3 NH3

6.6

-37.7

4 NH3 (2 en)

7.87 (13.86)

-44.9 (-79.1)

5 NH3

8.6

-49.1

6 NH3 (3 en)

8.61 (18.28)

-49.2 (-104.4)

74

2+

[Ni(H2O)6] + 6NH3
[Ni(NH3)6]2+
2+

+ 3en

2+

+ 3en

[Ni(H2O)6]
[Ni(NH3)6]

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6
3

2+

[Ni(NH3)6]
[Ni(H2O)6]2+ + 6NH3
2+

[Ni(en)3]

2+

[Ni(en)3] + 6NH3

75

An

alternative view comes from trying to

understand how the reactions might proceed.
To form a complex with 6 monodentates requires
6 separate favourable collisions between the metal
ion and the ligand molecules.
To form the tris-bidentate metal complex requires
an initial collision for the first ligand to attach by
one arm but remember that the other arm is always
going to be nearby and only requires a rotation of
the other end to enable the ligand to form the
chelate ring.
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76

If you consider dissociation steps, then when a

monodentate group is displaced it is lost into the

bulk of the solution.
On the other hand, if one end of a bidentate group
is displaced the other arm is still attached and it is
only a matter of the arm rotating around and it can
be reattached again.
Both sets of conditions favour the formation of the
complex with bidentate groups rather than
monodentate groups.
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Coordination chemistry
Reactions of Metal Complexes
77

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Ligand Substitution Reactions:

Octahedral Complexes
78

Inert & Labile Complexes

labile => exchange t1/2 less than 1 min. at RT

inert => exchange t1/2 more than 1 min. at RT

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Substitution reactions
MLn-1L' + L

MLn + L'

Labile complexes <==> Fast substitution reactions (< few min)

Inert complexes <==> Slow substitution reactions (>h)
a kinetic concept
Not to be confused with
stable and unstable (a thermodynamic concept Gf <0)

Inert

Intermediate

d3, low spin d4-d6& d8

d8 (high spin)

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79

Labile
d1, d2, low spin d4-d6& d7-d10

Mechanisms of ligand exchange reactions

in octahedral complexes

MLn Y+X

MLn X+Y
Dissociative (D)
MLn Y

MLn X

Associative (A)

MLn

MLn Y

MLn X
Y

MLn XY

Interchange (I)
MLn X

MLn Y

Ia if association
is more important
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[MLn]
X

80

Id if dissociation
is more important

Kinetics
of dissociative reactions

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81

Fast equilibrium
K1 = k1/k-1

Kinetics
of interchange reactions

k2 << k-1

For [Y] >> [ML5X]

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82

Kinetics of associative reactions

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83

Principal mechanisms of ligand exchange in octahedral complexes

Dissociative
ML5 X

k1
slow

ML5 +X
+Y

k2
fast

r=k 1[ML5X]
ML5 Y

Associative
ML5 X+Y

k1
slow

ML5 XY
X

k2
fast

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84

r=k 1[ML5X][Y]
ML5 Y

Dissociative pathway
(5-coordinated intermediate)

MOST COMMON

Associative pathway
(7-coordinated intermediate)

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85

Inert and labile complexes

Some common thermodynamic and kinetic profiles

Exothermic
(favored, large K)
Large Ea, slow reaction

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Exothermic
(favored, large K)
Large Ea, slow reaction
Stable intermediate

86

Endothermic
(disfavored, small K)
Small Ea, fast reaction

Labile or inert?
L
L
L

Ea
L

L
L
L

M
X

L
X

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87

L
L

Substitution reactions in square-planar complexes

the trans effect
L

X
M

+X, -Y

L
M
T

(the ability of T to labilize X)

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88

Y
L

Synthetic applications
of the trans effect

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89

Mechanisms of ligand exchange reactions in square planar complexes

+S

S
L
L

+Y

d[ML 3X]/dt=(k s+ky[Y])[ML 3X]

L
L

X
L
L

M
90

L
Y

L
S

M
+Y
Y

CHY4006 GRH

X
X

Y
L

L
S

Electron transfer (redox) reactions

-1e (oxidation)

M1(x +1)+Ln + M2(y-1)+Ln

M1(x+)Ln + M2(y+)Ln

+1e (reduction)

Very fast reactions (much faster than ligand exchange)

May involve ligand exchange or not
Very important in biological processes (metalloenzymes)
CHY4006 GRH

91

Outer sphere mechanism

[Fe(CN)6]3- + [IrCl6]3-

[Fe(CN)6]4- + [IrCl6]2-

[Co(NH3)5Cl]+ + [Ru(NH3)6]3+

[Co(NH3)5Cl]2+ + [Ru(NH3)6]2+

Reactions ca. 100 times faster

than ligand exchange
(coordination spheres remain the same)

"solventcage"

r = k [A][B]
Ea

Tunneling
mechanism

A'

G
CHY4006 GRH

92

B'

Inner sphere mechanism

[Co(NH3)5Cl)]2+:::[r(H2O)6]2+

[Co(NH3)5Cl)]2+ + [r(H2O)6]2+

[CoIII(NH3)5(-Cl)rII(H2O)6]4+

[Co(NH3)5Cl)]2+:::[r(H2O)6]2+

[CoII(NH3)5(-Cl)rIII(H2O)6]4+

[CoIII(NH3)5(-Cl)rII(H2O)6]4+

[CoII(NH3)5(-Cl)rIII(H2O)6]4+

[CoII(NH3)5(H2O)]2+ + [rIII(H2O)5Cl]2+

[CoII(NH3)5(H2O)]2+

CHY4006 GRH

[o(H2O)6]2+ + 5NH4+

93

Inner sphere mechanism

OxX+Red

k1

OxXRed

k2

Reactions much faster

than outer sphere electron transfer
(bridging ligand often exchanged)

k3
k4

Ox(H2O)+RedX+

Ox-X-Red

Tunneling
through bridge
mechanism

r = k [Ox-X][Red] k = (k1k3/k2 + k3)

Ea
Ox-X

Red

Ox(H 2O)- + Red-X+

G

CHY4006 GRH

94