Coordination Chemistry:

Reaction and Mechanisms

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 Reaction terms
• Transition-state theory describes chemical
No intermediate reactions as moving from one energy minimum
(the reactants) through higher energy structures
(transition states, intermediates) to another
energy minimum (the products).

• The highest energy structure along the reaction

pathway is called the transition State.

intermediate • An intermediate is formed along the reaction

pathway. Intermediates, unlike transition states,
are sometimes detectable.

• The presence of undetectable intermediates can allow

application of the steady-state approximation during
analysis of the reaction kinetics, in which the
concentration of the intermediate is assumed to be
extremely small and essentially unchanging during
much of the reaction.

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 Reaction terms

• Kinetics experiments are carried out to determine a number of parameters

that link to the reaction mechanism.

• The order of each reactant, indicated by the power of the reactant

concentration in the differential equation that describes how its
concentration changes with time, indicates how the reaction rate is tied to a
change in that reactant’s concentration.

• The rate constant, a proportionality constant that relates the reaction rate to
the concentrations of the reactants, is temperature dependent.
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 The Arrhenius Equation

The modern form of the Arrhenius equation shows the relationship between
the rate constant (k) and the temperature in kelvin (T):

In this equation:
• R is the gas constant (8.314 J /mol · K),
• A is a constant called the frequency factor (or the pre-exponential factor)
• Ea is the activation energy (or activation barrier).

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 The activation energy (Ea) is an energy barrier or hump that must be surmounted
in order for the reactants to transform into products.

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 The rate of chemical reaction
H2(gas) + I2(g) → 2HI (g)

The reaction rate is defined as the negative of the change in concentration of a

reactant divided by the change in time.

Reaction aA + bB → cC + dD

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 The Equilibrium Constant (K)

The equilibrium constant (K) for the reaction is defined as the ratio—at
equilibrium—of the concentrations of the products raised to their stoichiometric
coefficients divided by the concentrations of the reactants raised to their
stoichiometric coefficients:

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 The Rate Law: The Effect of Concentration on Reaction Rate

A → products
The rate law is the relationship between the rate of the reaction and the
concentration of the reactant.

𝑟𝑎𝑡𝑒 = 𝑘[𝐴]𝑛
where k is a constant of proportionality called the rate constant and n is the
reaction order.

The value of n (usually an integer) determines how the rate depends on the
concentration of the reactant:
o If n = 0, the reaction is zero order and the rate is independent of the
concentration of A.
o If n = 1, the reaction is first order and the rate is directly proportional to the
concentration of A.
o If n = 2, the reaction is second order and the rate is proportional to the square
of the concentration of A.
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 Order Reaction
Zero-Order Reaction
The rate of the reaction is independent of the concentration of the reactant:
Rate = k[A]0 = k
o The concentration of the reactant decreases linearly with time.
o Zero-order reactions occur under conditions where the amount of reactant
actually available for reaction is unaffected by changes in the overall quantity
of reactant

First-Order Reaction
The rate of the reaction is directly proportional to the concentration of the
reactant:
Rate = k[A]1
o The rate slows down as the reaction proceeds because the concentration of
the reactant decreases.

Second-Order Reaction
The rate of the reaction is proportional to the square of the concentration of
the reactant:
Rate = k[A]2
o The rate is even more sensitive to the reactant concentration.
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 𝑛
𝑟𝑎𝑡𝑒 = 𝑘[𝐴]

Reaction Coordinate Diagrams. (a), (b) Large activation energy hinders the
reaction rate even though the equilibrium favors the products since G < 0 ;
(c) Smaller activation energy facilitates a faster reaction, but the equilibrium
favors the reactants since G > 0. In (b), the intermediate is potentially
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 Substitution Reaction

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 Substitution Reaction

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PTK-IU 13
PTK-IU 14
 Copyright © 2014 Pearson Education, Inc.

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PTK-IU 16
 Labile compounds vs inert compounds
React rapidly React slowly

• Complexes such as [Cr(H2O)6]2+, which react rapidly, essentially

exchanging one ligand for another within the time of mixing the reactants,
are classified as labile.
• A labile complex has a very low activation energy for ligand substitution.

• Compounds that react more slowly are called inert. Within this context, an
inert compound does not resist ligand substitution; it is simply slower to
react, with a higher activation energy for ligand substitution.

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 Kinetic Consequences of Reaction Pathways
Dissociation (D)
• In a dissociative (D) reaction, the first step is loss of a ligand to form an
intermediate with a lower coordination number.
• Subsequent additions of either a new ligand (Y) or the leaving group (X) are two
possible reaction pathways for this intermediate:

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 Kinetic Consequences of Reaction Pathways
Dissociation (D)
Examination of the possibility of a D mechanism typically requires the steady-state
approximation. This approximation assumes that a vanishingly small (and constant)
concentration of the intermediate, ML5, is present during the reaction by assuming
that the rates of formation and consumption of the intermediate are equal.

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 Kinetic Consequences of Reaction Pathways
Dissociation (D)

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 Kinetic Consequences of Reaction Pathways
Association (A)
In an associative reaction, forming an intermediate with an increased coordination
number is the rate-determining step. This first step is followed by a faster reaction
in which the exiting ligand is lost:

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 Preassociation Complexes

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 Kinetic Consequences of Reaction Pathways
Interchange (I)
An interchange (I) reaction in its simplest form is a direct replacement of the
leaving group with the incoming group that does not proceed via an intermediate,
but rather a single transition state leading to the conversion of reactants to
products.

irreversible

reversible

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Id, dissociative interchange vs Ia, associative interchange
Interchange (I)
• Two variations on the interchange mechanism are Id, dissociative
interchange, and Ia, associative interchange.

• The difference is the relative strengths of the M—X and M—Y bonds
in the transition state.

• If bonding between the incoming ligand and the metal is more

important in the transition state, it is an Ia mechanism. M—Y >
transition state

• If breaking the bond between the departing ligand and the metal is
more important in the transition state, it is an Id mechanism. M—X >
transition state

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 Summary
The stability of the intermediate of ligand substitution.

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 Experimental Evidence in Octahedral Substitution
Dissociation
• The ligand field activation energy (LFAE), defined as the difference between the
LFSE (ligand field stabilization energy) of the square-pyramidal transition state and
the LFSE of the octahedral reactant.
• LFAEs for trigonal-bipyramidal transition states are generally the same or larger than
those for square-pyramidal transition states

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 Experimental Evidence in Octahedral Substitution
The highest (most positive) LFAE values are The negative LFAE parameters
associated with d3 and low-spin d4, d5, and d6; all predict low activation barriers for
of these ions are classified as inert, supported by dissociation, and are associated with
the predicted relatively high activation barriers for ions classified as labile.
ligand dissociation from octahedral complexes of
these ions.

This approach fares poorly with d8 ions, but these ions generally do not form
PTK-IU octahedral complexes. 28
 Geometries and crystal field splitting diagrams

Octahedral

Pentagonal
bipyramidal

Square antiprismatic

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 Geometries and crystal field splitting diagrams
Square planar

Square pyramidal

Tetrahedral

Trigonal
bipyramidal

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 Ligand Field Stabilization Energy

If the metal were surrounded by a spherical field of electrons, then all of the
electrons on the metal would be raised equally high in energy by these repulsive
forces.

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 Ligand Field Stabilization Energy
in a metal salt, electrons are not approaching the metal from all directions. The
geometry comes in because of the fact that the cations and anions pack together
in specific arrays.
For example, if a metal cation is sitting in an octahedral hole, electrons would only
approach from six directions: at each end of the x, y, and z axes.

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 Ligand Field Stabilization Energy
only the electrons in d orbitals that were aligned along the x, y and z axes would
be raised significantly by repulsion with the approaching electrons on the anions.
The electrons in the off-axis orbitals would be lower in energy than they would
have been in a perfectly spherical field.

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 Ligand Field Stabilization Energy

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 Ligand Field Stabilization Energy

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 Ligand Field Stabilization Energy
LFSE
0

-0.5

-1
Energy (Δ)

-1.5

-2

-2.5

-3
0 1 2 3 4 5 6 7 8 9 10
d electron

Low-spin LFSE High-spin LFSE

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 Crystal Field Stabilization Energy
The Crystal Field Stabilization Energy is defined as the energy of the electron
configuration in the ligand field minus the energy of the electronic
configuration in the isotropic field.

CFSE=ΔE= Eligand field−Eisotropic field

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 Crystal Field Stabilization Energy
a high Spin d7

a low Spin d7

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 Crystal Field Stabilization Energy
Total d- Crystal Field Stabilization
Isotropic Field Octahedral Complex
electrons Energy

High Spin Low Spin

Eisotropic
Eligand Eligand
fieldEisotropic Configuration Configuration High Spin Low Spin
fieldEligand field fieldEligand field
field

d0 0 t2g0eg0 0 t2g0eg0 0 0 0

d1 0 t2g1eg0 -2/5 Δo t2g1eg0 -2/5 Δo -2/5 Δo -2/5 Δo

d2 0 t2g2eg0 -4/5 Δo t2g2eg0 -4/5 Δo -4/5 Δo -4/5 Δo

d3 0 t2g3eg0 -6/5 Δo t2g3eg0 -6/5 Δo -6/5 Δo -6/5 Δo

d4 0 t2g3eg1 -3/5 Δo t2g4eg0 -8/5 Δo + P -3/5 Δo -8/5 Δo + P

d5 0 t2g3eg2 0 Δo t2g5eg0 -10/5 Δo + 2P 0 Δo -10/5 Δo + 2P

d6 P t2g4eg2 -2/5 Δo + P t2g6g0 -12/5Δo + 3P -2/5 Δo -12/5 Δo + P

d7 2P t2g5eg2 -4/5 Δo + 2P t2g6eg1 -9/5Δo + 3P -4/5 Δo -9/5 Δo + P

d8 3P t2g6eg2 -6/5 Δo + 3P t2g6eg2 -6/5 Δo + 3P -6/5 Δo -6/5 Δo

d9 4P t2g6eg3 -3/5 Δo + 4P t2g6eg3 -3/5 Δo + 4P -3/5oΔo -3/5 Δo

d10 5P t2g6eg4 0 Δo + 5P t2g6eg4 0 Δo + 5P 0 0

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 Experimental Evidence in Octahedral Substitution
Dissociation
Electronic and steric factors also influence substitution reaction rates of
octahedral complexes. The inequalities below indicate relative rates for
ligand exchange via presumed dissociative mechanisms.

1. Oxidation state of the central ion. Central atoms with higher oxidation
states have slower ligand exchange rates.

2. Ionic radius. Smaller ions have slower exchange rates.

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 Linear Free-Energy Relationships
• Kinetic effects are related to thermodynamic effects by linear free-energy
relationships (LFER)

• The bond strength of a metal-ligand bond (a thermodynamic function vs the

dissociation rate of that ligand (a kinetic function).

• In molecular bonding term, a stronger bond between the metal and the
leaving group results in a larger activation energy.

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 Linear Free-Energy Relationships

Linear Free Energy

Relationship for [Co(NH3)5X]2+
Hydrolysis at 25.0 °C (X
indicated at each point). The
log of the rate constant is
plotted against the log of the
equilibrium constant for the
acid hydrolysis reaction of
[Co(NH3)5X]2+ ions.

the equilibrium constant (thermodynamic) vs the rate constant

has to be linear relationship
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 • For the first-order region (large [Y]); The rate constant are all
relatively close to that for water exchange → dissociative
mechanism
• The k1 column gives the rate constants for anion exchange
• the k1/k1(H2O) shows the ratio of k1 to the rate for water exchange.
 k1(H2O) ~ 100 x 10-6 s-1 : constant
• The rate constants do not vary significantly with the substituting
anion, as would be expected for a dissociative mechanism.

Copyright © 2014 Pearson Education, Inc.

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 • The second-order region for anation of [Ni(H2O)6]2+: a preassociation mechanism.

• The second-order rate constant, k2K1, is the product of the ion-pair equilibrium
constant, K1, and the rate constant, k2
• The rate constants, k2, vary by a factor of 5 or less and are close to the rate
constant for water exchange.
• The close agreement for different ligands Y shows that the effect of the incoming
ligand is minor, although the difference in ion-pair formation is significant. These
data are most consistent with a preassociation mechanism.

Copyright © 2014 Pearson Education, Inc.

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 Associative Mechanisms
• Associative reactions are less common with octahedral complexes.

• The [Cr(NH3)5(H2O)]3+ complex with the more electron rich Cr(III) center appears less
reactive towards initial binding of an incoming nucleophile relative to [Cr(H2O)6]3+

• The varying amount of electron density at the Cr(III) centers of these complexes due to
the increased donation of ammonia relative to water plays a significant role in
determining both the substitution mechanism and the reaction rate.

10-4 10-8

Id, dissociative Ia, associative

interchange interchange

Rate constants
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 Associative Mechanisms

Pyrazine Isonicotinamide Pyridine Imidazole

Reactions of Ru(III) compounds frequently have associative interchange mechanisms

Note: high density electron of nitrogen compounds enhances the interaction with
PTK-IU central metal atom (Ru(III)), Ru-new ligand > Ru-old ligand 46
 Associative Mechanisms

H3C − CN

Isonicotinamide

Reactions of Ru(II) compounds generally have dissociative interchange mechanisms

Rate constants
Copyright © 2014 Pearson Education, Inc.
are similar
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 The Conjugate Base Mechanism
• Some cases in which second-order kinetics suggest an associative
mechanism are believed to proceed via a conjugate base mechanism,
called SN1CB for substitution, nucleophilic, unimolecular, conjugate base.
• These reactions depend on amine, ammine (NH3), or aqua ligands that
can be deprotonated to form amido or hydroxo species that subsequently
release a ligand dissociatively.
• The ligand trans to the amido or hydroxo group that dissociates.

1. Base catalyzed exchange of hydrogen from the amine groups

takes place under the same conditions.
2. RNH2 compounds react fast than NH3. (help to form 5-coordinate)
3. When substituted amines used (no protons), the reaction is very
slow or nonexistent.
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 The Conjugate Base Mechanism
a trigonal-
bipyramidal
geometry
Trans
(faster)

104 times faster Less activation energy

cis

A square-
pyramidal
structure

Base Hydrolysis of [Co(tren)(NH3)Cl]2+ Isomers.

(a) Leaving group (Cl−) trans to deprotonated nitrogen.
(b) Leaving group (Cl−) cis to deprotonated nitrogen.
PTK-IU (Data from D. A. Buckingham, P. J. Creswell, A. M. Sargeson, Inorg. Chem. , 1975 , 14 , 1485.) 49
 The Kinetic Chelate Effect
• The chelate effect causes polydentate complexes to be thermodynamically more stable
than their monodentate counterparts.
• Substitution for a chelated ligand is generally a slower reaction than that for a similar
monodentate ligand.
• Explanations for this effect center on two factors. First, the ΔH associated with removal of the first bound
atom is larger than for a related monodentate ligand. If this atom does separate from the metal center, its
kinetic barrier for subsequent reattachment is lower than for a related monodentate ligand since the former
remains in close proximity to the metal center.

The increased energy

needed to remove the
first bound atom and the
probability of a reversal
of this first step
The ligand must bend
and rotate to move the
free amine group away
from the metal.

The concentration of
the intermediate is
low and the first
dissociation can
readily reverse
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 Stereochemistry of Reactions
• The conjugate base mechanism is proposed, with hydroxide removing a proton
from an ethylenediamine nitrogen, followed by chloride loss trans to the amido
ligand.
• In more concentrated base, ion pairs ([Co(en)2Cl2]+ · OH –) are assumed to result
in a water molecule (from the OH– and the H+ removed from ethylenediamine),
positioned for facile addition for inversion of the chiral center.

Mechanisms of Base Hydrolysis of Λ-cis-[Co(en)2Cl2]+.

(a) Retention of configuration in dilute hydroxide.
(b) Inversion of configuration in concentrated hydroxide.
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 Substitution in trans Complexes
Dissociation Mechanism and Stereochemical Square-pyramidal intermediate
Changes for trans - [M(LL)2BX]. (a) Square-
pyramidal intermediate (retention of configuration).
(b) Trigonal-bipyramidal intermediate (while only
formation of the isomers is shown, a racemic mixture
of cis isomers is expected since Λ and Δ trigonal-
bipyramidal intermediate are equally likely upon X
dissociation). (c) Less likely trigonal-bipyramidal
intermediate (two possible products).
1
2 3
• (a) If dissociation of X from the reactant leaves a Trigonal bipyramidal
intermediate with
square-pyramidal intermediate that adds the new B in the trigonal
ligand to the vacant site, the result is retention of plane
configuration, and the product, like the reactant,
is trans.
• (b) A trigonal-bipyramidal intermediate with B in
the trigonal plane leads to a mixture of trans and
cis. Trigonal bypyramidal
• (c) Dissociation to form a trigonal pyramid with intermediate with B in
the axial position
B in an axial position allows two positions for
attack by Y, both of which give cis products (the
third side of the triangle is blocked by an LL ring)

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 Substitution in cis Complexes
Dissociation Y Mechanism and Stereochemical
Changes for cis-[M(LL)2BX]. (a) Square-pyramidal
intermediate (retention of configuration). (b)
Trigonal-bipyramidal intermediate. (c) Unlikely
trigonal bipyramidal intermediate.

• Substitution in cis complexes can also

proceed by three intermediates

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 Substitution in cis Complexes
• As a general rule, cis reactants give a relatively higher percentage of substitution
products that retain their cis configuration;
• trans reactants often afford a more balanced mixture of cis and trans substitution
products.
• The variety of factors that interplay to govern product mixtures require a significant
amount of data to formulate mechanistic hypotheses

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 Substitution Reactions of Square-Planar Complexes
Kinetics and Stereochemistry of Square-Planar Substitutions
T– Pt–X + Y → T–Pt–Y + X
T is the ligand trans to the departing
ligand X, and Y is the incoming ligand

Ia

Id

where [Cplx] = concentration of the reactant complex and [Y] = concentration of the
incoming ligand.
The k2 term fits a standard associative mechanism, the k1 term is a solvent-assisted
PTK-IU reaction, with solvent. 60
 Evidence for Associative Reactions
This mechanism reveals an effect of the incoming ligand. Pt(II) is a soft acid, so
soft ligands react more readily with it.

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 • The leaving group X, the other species in the trigonal plane of the 5-coordinate
intermediate also has a significant influence on the rate
• Hard ligands such as Cl-, NH3, and NO3- leaving relatively quickly.
• Soft ligands with considerable metal-to-ligand π bonding, such as CN- and NO2-, leave
relatively slowly

Pt(II) is a
soft acid

Hard ligands

Soft ligands

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 The trans Effect
• the trans effect in platinum chemistry.
• In reactions of square-planar Pt(II)
compounds, ligands trans to chloride are
more easily replaced than those trans to
ammonia; chloride has a stronger trans
effect than ammonia.
• The trans effect allows the formation of
isomeric Pt compounds

Stereochemistry and the trans Effect in Pt(II)

Reactions. Charges have been omitted for clarity. In
(a) through (f), the first substitution can be at any
position, with the second controlled by the trans
effect. In (g) and (h), both substitutions are
controlled by the lability of chloride.

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 Oxidation–Reduction Reactions
• Oxidation–reduction reactions of transition-metal complexes involve electron
transfer from one complex to another.
• The two molecules may be connected by a common ligand through which the
electron is transferred (inner-sphere reaction), or the exchange may occur
between two separate coordination spheres (outer-sphere reaction).
• Electron transfer rates depend on the rate of ligand substitution within the
reactants, the match of the reactant orbital energies, solvation of reactants, and
the nature of the ligands.

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 Oxidation–Reduction Reactions
Inner-Sphere Reaction
• Inner-sphere reactions use the tunneling phenomenon with a ligand as the
conduit.
• Inner sphere electron transfer the participating redox sites undergoing
electron transfer become connected by a chemical bridge.
• These reactions proceed in three steps:
(1) a substitution reaction that leaves the oxidant and reductant linked by a
bridging ligand;
(2) the electron transfer, frequently accompanied by transfer of the ligand;
(3) separation of the products:

[Co(NH3)5(Cl)]2+ + [Cr(H2O)6]2+→[(NH3)5Co(Cl)Cr(H2O)5]4+ + H2O (1)

Co(III) oxidant Cr(II) reductant Co(III) Cr(II)

[(NH3)5Co(Cl)Cr(H2O)5]4+ → [(NH3)5Co(Cl)Cr(H2O)5]4+ (2)

Co(III) Cr(II) Co(II) Cr(III)

[(NH3)5Co(Cl)Cr(H2O)5]4+ + H2O →[(NH3)5Co(H2O)]2+ + [(Cl)Cr(H2O)5]2+ (3)

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 Inner-Sphere Reaction

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 Oxidation–Reduction Reactions
Outer-Sphere Reactions
Outer sphere refers to an electron transfer
(ET) event that occurs between chemical
species that remain separate and intact
before, during, and after the ET event.

https://en.wikipedia.org/wiki/Outer_sphere_electron_transfer
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 Oxidation–Reduction Reactions
• The delocalized π systems of the bipy ligands of [Cr(bipy)3]2+ may lower the barrier
for outer-sphere electron transfer relative to [Ru(NH3)6]2+;
• Metal to ligand charge transfer in [Cr(bipy)3]2+ may facilitate the electron transfer.

>
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 Oxidation–Reduction Reactions
Outer-sphere electron transfer
• It has been hypothesized that the thermodynamic stability of the EuX+ species
increases as the halide size decreases, with slower rates and lower stabilities
as we go down the series.
• Because of the smaller range of rate constants, Eu2+ reactions are usually
classified as outer-sphere.
an outer-sphere mechanism is more likely with V2+.

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 Oxidation–Reduction Reactions
[Co(CN)5]3- reacts with Co(III) oxidants ([Co(NH3)5X]2+) that have halide
ligands as bridging candidates, the product is [Co(CN)5X]3-, evidence for
an inner-sphere mechanism. an outer-sphere mechanism
an inner-sphere mechanism because ammonia cannot bridge

[Co(NH3)6]2+

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 Oxidation–Reduction Reactions
inner-sphere mechanisms
• Reactions exhibit inner-sphere mechanisms, with formation of a bridging
carboxylate, and Cr(II) bridging via the L carbonyl oxygen.
• The difference in rates reflects the electron transfer rates.
• Electron transfer through bridging ligands is faster when those ligands are more
easily reduced.

PTK-IU 73
 Oxidation–Reduction Reactions
• The rate for Co compounds with other bridging ligands is frequently as much as 105
faster than the rate for corresponding Cr compounds, because of the greater
oxidizing power of Co(III).
• The much faster rate found for the ruthenium pentaammine has been explained as
the result of the transfer of an electron through the π system of the ligand into the t2g
levels of Ru(III); low-spin Ru(III) has a vacancy in the t2g level.

PTK-IU 74
 Conditions for High and Low Oxidation Numbers
• The overall stability of complexes with different charges on the metal ion
depends on the LFSE, metal-ligand bonding, and redox properties of the
ligands.

• All the very high oxidation numbers for the transition metals are found
in combination with hard ligands, such as fluoride and oxide.
• Examples include MnO4- , CrO42-, and FeO42- with oxide, and RuF5,
PtF6, and OsF6 with fluoride.

• The lowest oxidation states are found with soft ligands.

• Example: Extremely soft zerovalent metals are often found in
complexes with carbonyl ligands; V(CO)6, Cr(CO)6, Fe(CO)5,
Co2(CO)8, and Ni(CO)4

PTK-IU 75
 Conditions for High and Low Oxidation Numbers
Borderline acid Soft acid
• High Cu(II) oxidation state vs low Cu(I) and Cu(0) oxidation states
• Soft ligand: I– > Cl–
• The reduction potentials for Co(III)–Co(II) with different ligands are in the
order H2O > NH3 > CN– because the stability of Co(III) with ligand is reverse.

soft
ligand

hard
ligand

Increase
decrease
stability

PTK-IU 76