Lec.

1: Reaction Mechanisms in Coordination and Organometallic Chemistry

Content:
1. Introduction
2. Substitution Reactions - Inertness and Lability
3. Classification of Reaction Mechanisms in Inorganic Chemistry involving Metal
4. Kinetic Consequences of the Reaction Pathways

1) Introduction

The term reaction mechanism refers to the specific sequence of elementary reactions leading to an
overall chemical change. Inorganic chemistry has always lagged behind organic chemistry in
determination of reaction mechanisms. The first ideas of the mechanisms of organic reactions started
to develop around 1920. The mechanistic considerations of organic reactions in solutions were
primarily applied to the reactions of tetrahedral and trigonal planar carbon atoms. This is because
organic compounds often undergo reactions at one center, while the other bonds suffer minor changes
or practically do not change at all. Organic reactions are very versatile. Their rates can be easily varied
by changing the reaction conditions in order to get rates that can be followed by conventional kinetic
techniques available at the time. On the other hand, inorganic reactions are often very fast and
therefore less favorable for kinetic studies.

In 1891 Werner (Nobel Prize 1913) put forward his coordination theory, which permitted a simple
classification of inorganic compounds and extended the concept of isomerism. His views have
remained fundamental to modern inorganic chemistry and have paved the way for modern concepts of
chemical bonding.

The progress of chemistry of metal complexes, notably the development of metallo-organic and
bioinorganic chemistry, enabled the kinetic studies of octahedral complexes of cobalt (III), for instance
[Co(NH3)6]3+, and of square-planar complexes, such as [PtCI 4]2-, and also of tetrahedral complexes, for
instance [CuBr4]2- and several others.

Physical and theoretical chemistry started to penetrate equally into organic and inorganic chemistry,
and the borders between these two fields began to disappear. Thus, organic and inorganic chemistry
are nowadays equally meritorious for the broadening of our knowledge of reaction mechanisms in
general.

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Reactions of coordination complexes can be conveniently divided into substitution reactions at the
metal center, oxidation-reduction reactions, and reactions of the ligands that do not change the
attachments to the metal center. Reactions that include more elaborate rearrangements of ligand
structures are more often observed in organometallic compounds (to be described later).

Generally, chemical reactions move from one energy minimum (the reactants) through a higher energy
structure (the transition state) to energy minimum (the products). In simple cases, the energies and
bond distances can be shown as a three dimensional surface, with two different bond distances along
the base-plane axes and free energy as the vertical dimension. The reaction:

MX + Y→MY + X,

begins at a point representing the short M-X distance of the bond to be broken and the longer distance
between the two reactants MX and Y. As the M-X bond breaks and the M-Y bond forms, the reaction
point moves to represent the short M-Y bond distance and the longer distance between the two
products MY and X. The free energy surface usually has a saddle shape, much like a mountain pass
between two valleys. For more complex reactions, such a visual representation is difficult or
impossible, but the path between the reactants and the products is always the lowest energy pathway
and must be the same regardless of the direction of the reaction. This is the principle of microscopic
reversibility, frequently described by the mountain pass analogy; the lowest pass going in one
direction must also be the lowest pass going in the opposite direction.

If the reaction is such that the conversion from reactants to products takes place with no hesitation at
the transition point as in Figure 1(a), the structure at that state is called the transition state. If there is
a structure that lasts a bit longer as in Figure l(b), and particularly if it is detectable by some
experimental means, it is called an intermediate. Frequently, the kinetic equations include
intermediates, even if they remain undetected. Their presence allows treatment by a steady-state
approximation, in which the concentration of the intermediate is assumed to be small and essentially
unchanging during much of the reaction.

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FIGURE 1 Energy Profiles and Intermediate Formation. (a) No intermediate. The activation energy is the energy difference
between the reactants and the transition state. (b) An intermediate is present at: ' the small minimum at the top of the curve.
The activation energy is measured at the maximum point of the curve.

A number of different parameters can be obtained from kinetics experiments. First, the order of the
reaction, indicated by the power of the reactant concentration in the differential equation that describes
it, can be determined, together with the rate constant that describes the speed of the reaction. By
studying a reaction at different temperatures, the free energy of activation and the enthalpy (or heat)
and entropy of activation can be found. These allow further interpretation of the mechanism and the
energy surface. A somewhat more recent inclusion of pressure dependence provides the volume of
activation, which offers insight into whether the transition state is larger or smaller than the reactants.

2) Substitution Reactions - Inertness and Lability

Many synthetic reactions require substitution, or replacing one ligand by another; this is particularly
true when the starting material is in aqueous solution, where the metaI ion is likely to be in the form
[M(H2O)m]n+. Some simpler reactions of this type produce colored products that can be used to identify
metal ions:

These reactions, and others like them, are very fast and form species that can undergo a variety of
reactions that are also very fast. Addition of HNO 3(H+), NaCI(C1-), H3PO4 ( PO43-) , KSCN(SCN-), and

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NaF(F-) successively to a solution of Fe(NO3)3.9 H2O shows this very clearly. The initial solution is
yellow because of the presence of [Fe(H 2O)5(OH)]2+ and other "hydrolyzed" species containing both
water and hydroxide ion. Although the exact species formed in this series depend on solution,
concentrations, the products in the reactions given here are representative:

Compounds such as these that react rapidly are called labile. In many cases, exchange of one ligand
for another can take place in the time of mixing the solutions. Taube (1952) has suggested a reaction
half-life (the time of disappearance of half the initial compound) of one minute or less as the criterion
for lability. Compounds that react more slowly are called inert or robust (a term used less often). An
inert compound is not inert in the usual sense that no reaction can take place; it is simply slower to
react. These kinetic terms must also be distinguished from the thermodynamic terms stable and
unstable. A species such as [Fe(H2O)5(F)]2+ is very stable (has a large equilibrium constant for
formation), but it is also labile. On the other hand, hexaaminecobalt (3+) is thermodynamically
unstable in acid and can decompose to the equilibrium mixture on the right

but it reacts very slowly (has a very high activation energy) and is therefore called inert or robust. The
possible confusion of terms is unfortunate, but no other terminology has gained general acceptance.
One possibility is to call the compounds substitutionally or kinetically labile or inert, but these terms
are not in general use at this time.
Werner studied cobalt(III), chromium(III), platinum(II), and platinum(1V) compounds because they
are inert and can be more readily characterized than labile compounds. This tendency has continued,

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and much of the discussion in this chapter is based on inert compounds because they can be more
easily crystallized from solution and their structures determined. Labile compounds have also been
studied extensively, but their study requires techniques capable of dealing with very short times
(stopped flow or relaxation methods, for example, temperature or pressure jump, nuclear magnetic
resonance).

Although there are exceptions, general rules can be given for inert and labile electronic structures

-The first general rule is that complexes of metals that have no additional factor to provide extra
stability (for instance, the LFSE and chelate effects) are among the most labile. Any additional
stability of a complex results in an increase in activation energy for a ligand replacement reaction and
hence decreases the lability of the complex.

- A second general rule is that very small ions are often less labile because they have greater M-L bond
strengths and it is sterically very difficult for incoming ligands to approach the metal atom closely.
Some further generalizations are as follows:
1. All complexes of s-block ions except the smallest (Be2+ and Mg2+) are very labile.
2. Complexes of the M(III) ions of the f block are all very labile.
3. Complexes of the d10 ions (Zn2+, Cd2+, and Hg2+) are normally very labile.
4. Across the 3d series, complexes of d-block M(II) ions are generally moderately labile, with
distorted Cu(II) complexes among the most labile.
5. Complexes of d-block M(III) ions are distinctly less labile than d-block M(II) ions.
6. d-Metal complexes with d3 and low-spin d6 configurations (for example Cr(III), Fe(II), and Co(III))
are generally non-labile as they have large LFSEs. Chelate complexes with the same configuration,
such as [Fe(phen)3]2+, are particularly inert.
7. Non-lability is common among the complexes of the 4d and 5d series, which reflects the high LFSE
and strength of the M-L bonding.
Table 1 below illustrates the range of timescales for a number of reactions.

Table 1 Representative timescales of chemical and physical processes

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The natures of the ligands in the complex also affect the rates of reactions. The identity of the
incoming ligand has the greatest effect, and equilibrium constants of displacement reactions can be
used to rank ligands in order of their strength as Lewis bases. However, a different order may be found
if bases are ranked according to the rates at which they displace a ligand from the central metal ion.
Therefore, for kinetic considerations, we replace the equilibrium concept of basicity by the kinetic
concept of nucleophilicity, the rate of attack on a complex by a given Lewis base relative to the rate
of attack by a reference Lewis base. The shift from equilibrium to kinetic considerations is emphasized
by referring to ligand displacement as nucleophilic substitution (SN).
Ligands other than the entering and leaving groups may play a significant role in controlling the rates
of reactions; these ligands are referred to as spectator ligands.

For instance, it is observed for square-planar complexes that the ligand trans to the leaving group X
has a great effect on the rate of substitution of X by the entering group Y.

Summarily, we get:

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3) Classification of Reaction Mechanisms in Inorganic Chemistry involving Metal Complexes
(a) (Dissociative, D [or SN1], Associative, A [or SN2], Interchange, I [Id & Ia]

The mechanism of a nucleophilic substitution reaction is the sequence of elementary steps by which
the reaction takes place and is classified as associative, dissociative, or interchange; an associative
mechanism is distinguished from an interchange mechanism by demonstrating that the intermediate
has a relatively long life.
The first stage in the kinetic analysis of a reaction is to study how its rate changes as the
concentrations of reactants are varied. This type of investigation leads to the identification of rate
laws, the differential equations governing the rate of change of the concentrations of reactants and
products. For example, the observation that the rate of formation of [Ni(NH3)(OH2)5]2+ from
[Ni(OH2)6]2+ is proportional to the concentration of both NH3 and [Ni(OH2)6]2+ implies that the reaction
is first order in each of these two reactants, and that the overall rate law is:

(1)

A note on good practice In rate equations, as in expressions for equilibrium constants, we omit the
brackets that are part of the chemical formula of the complex; the surviving brackets denote molar
concentration. We denote rate constants by kr, to avoid possible confusion with Boltzmann’s constant.

In simple sequential reaction schemes, the slowest elementary step of the reaction dominates the
overall reaction rate and the overall rate law, and is called the rate-determining step.
However, in general, all the steps in the reaction may contribute to the rate law and affect its rate.
Therefore, in conjunction with stereochemical and isotopic labelling studies, the determination of the
rate law is the route to the elucidation of the mechanism of the reaction.
Three main classes of reaction mechanism have been identified. A dissociative mechanism, denoted
D, is a reaction sequence in which an intermediate of reduced coordination number is formed by the
departure of the leaving group:

Here MLn (the metal atom and any spectator ligands) is a true intermediate that can, in principle, be
detected (or even isolated). The typical form of the corresponding reaction profile is shown in Fig.2a.

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.

Figure 2a The typical form of the reaction profile of a

reaction with a dissociative mechanism..

Example: The substitution of hexacarbonyltungsten by phosphine takes place by dissociation of CO from the
complex. W(CO)6 → W(CO)5 CO

followed by coordination of phosphine:

W(CO)5PPh3 → W(CO)5(PPh3)
Under the conditions in which this reaction is usually performed in the laboratory, the intermediate
W(CO)5 is rapidly captured by the solvent, such as tetrahydrofuran, to form [W(CO)5(thf)]. This
complex in turn is converted to the phosphine product, presumably by a second dissociative process.

-An associative mechanism, denoted A, involves a step in which an intermediate is formed

with a higher coordination number than the original complex:

Once again, the intermediate MLnXY can, in principle at least, be detected. This mechanism plays a
role in many reactions of square-planar Au(III), Pt(II), Pd(II), Ni(II), and Ir(I) d8 complexes. The
typical form of the reaction profile is similar to that of the dissociative mechanism, and is shown in
Fig.2b.

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 Figure 2b The typical form of the reaction profile of a
reaction with an associative , A, or SN2 mechanism.

Example. The first step in the exchange of 14CN with the ligands in the square-planar complex
[Ni(CN)4]2+ is the coordination of a ligand to the complex:

[Ni(CN)4]2+ + 14CN- → [Ni(CN)4(14CN)]3-

A ligand is then discarded:

[Ni(CN)4(14CN)]3- → [Ni(CN)3(14CN)]2- + CN-
The radioactivity of carbon-14 provides a means of monitoring this reaction, and the intermediate
[Ni(CN)5]3+ has been detected and isolated.

-An interchange mechanism, denoted I, takes place in one step:

MLnX + Y → X…….MLn ……Y → MLnY + X

The leaving and entering groups exchange in a single step by forming a transition state but not a true
intermediate. The interchange mechanism is common for many reactions of six-coordinate complexes.
The typical form of the reaction profile is shown in Fig. 2c.

Figure 2c The typical form of the reaction profile of a reaction with an

interchange , I, mechanism.

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Direct spectroscopic detection of the intermediate, and hence an indication of A rather than I, may be
possible if a sufficient amount accumulates. Such direct evidence, however, requires an unusually
stable intermediate with favourable spectroscopic characteristics.

b) The rate-determining step(rds)

-The rate-determining step is classified as associative or dissociative according to the dependence of
its rate on the identity of the entering group.
Now we consider the rate-determining step of a reaction and the details of its formation.
The step is called associative and denoted a if its rate depends strongly on the identity of the incoming
group. Examples are found among reactions of the d8 square-planar complexes of Pt(II), Pd(II), and
Au(III), including
[PtCl(dien)](aq) + I-(aq) → [PtI(dien)](aq) + Cl-(aq)
where dien is diethylenetriamine (NH2CH2CH2NHCH2CH2NH2). It is found, for instance, that use of I-
instead of Br- increases the rate constant by an order of magnitude. Experimental observations on the
substitution reactions of square-planar complexes support the view that the rate-determining step is
associative.
The strong dependence of the rate-determining step on entering group Y indicates that the transition
state must involve significant bonding to Y. A reaction with an associative mechanism (A) will be
associatively activated (a) if the attachment of Y to the initial reactant MLnX is the rate-determining
step; such a reaction is designated Aa, and in this case the intermediate MLnXY would not be detected.
A reaction with a dissociative mechanism (D) is associatively activated (a) if the attachment of Y to
the intermediate MLn is the rate-determining step; such a reaction is designated Da. Figure 3 shows the
reaction profiles for associatively activated A and D mechanisms. For the reactions to proceed, it is
necessary to have established a population of an encounter complex XM, Y in a pre-equilibrium step.
The rate-determining step is called dissociative and denoted d if its rate is largely independent of the
identity of Y. This category includes some of the classic examples of ligand substitution in octahedral
d-metal complexes, including:

It is found that replacement of NH3 by pyridine in this reaction changes the rate by at most a few per cent.

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Figure 3 The typical form of the reaction profile of reactions with an associatively activated step: (a)
associative mechanism, Aa; (b) a dissociative mechanism, Da

The weak dependence on Y of a dissociatively activated process indicates that the rate of formation of
the transition state is determined largely by the rate at which the bond to the leaving group X can
break. A reaction with an associative mechanism (A) will be dissociatively activated (d) provided the
loss of X from the intermediate YMLnX is the rate determining step; such a reaction is designated Ad.
A reaction with a dissociative mechanism (D) is dissociatively activated (d) if the initial loss of X from
the reactant MLnX is the rate-determining step, such a reaction is designated Dd. In this case, the
intermediate MLn would not be detected. Figure 4 shows the reaction profiles for dissociatively
activated A and D mechanisms.

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 Figure 4 The typical form of the reaction
Figure 5 The typical form of the reaction profile of reactions with
an interchange mechanism: (a) associatively activated, Ia; (b)
profile of reactions with a dissociatively activated
dissociatively activated, Id
step: (a) an associative mechanism, Ad;

A reaction that has an interchange mechanism (I) can be either associatively or dissociatively
activated, and is designated either Ia or Id, respectively. In an Ia mechanism, the rate of reaction
depends on the rate at which the M…Y bond forms, whereas in an Id reaction the rate of reaction
depends on the rate at which the M…X bond breaks (Fig. 5).
The distinction between these possibilities may be summarized as follows, where MLnX denotes the
initial complex:

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4) Kinetic Consequences of the Reaction Pathways

In the following reactions, X will indicate the ligand that is leaving a complex, Y the ligand that is
entering and L any ligands that are unchanged during the reaction. In cases of solvent exchange, all
(X, Y, and L) may be chemically the same species, but in the more general case they may all be
different.

I- DISSOCIATION (D)

In a dissociative (D) reaction, loss of a ligand to form an intermediate with a lower coordination
number is followed by addition of a new ligand to the intermediate:

The stationary-state (or steady-state) hypothesis assumes a very small concentration of the
intermediate, ML5 and requires that the rates of formation and reaction of the intermediate must be
equal. This in turn requires that the rate of change of [ML5] be zero during much of the reaction.
Expressed as a rate equation,

Solving for [ML5],

and substituting into the rate law for formation of the product,

leads to the rate law:

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One criterion for this mechanism is that the intermediate, ML5, be detectable during the reaction.
Direct detection at the low concentrations expected is a very difficult experimental challenge, and
there are very few clear-cut dissociative reactions. More often, the evidence is indirect, but no
intermediate has been found. Such reactions are usually classified as following an interchange
mechanism.

2- INTERCHANGE (I)

In an interchange (I) reaction, a rapid equilibrium between the incoming ligand and the 6-coordinate
reactant forms an ion pair or loosely bonded molecular combination. This species, which is not
described as having an increased coordination number and is not directly detectable, then reacts to
form the product and release the initial ligand.

When k2 << kl, the reverse reaction of the first step is fast enough that this step is independent of the
second step, and the first step is an equilibrium with K1 = kl/k-l.
Applying the stationary-state hypothesis:

If [Y] is large compared with [ML 5X] (a common experimental condition), the concentration of the
unstable transition species may be large enough to significantly change the concentration of the ML 5X,
but not that of Y. For this reason, we must solve for this species in terms of the total initial reactant
concentrations of ML5X and Y, which we will call [M]o and [Y]o:

Assuming that the concentration of the final product, [ML 5Y], is too small to i, change the
concentration of Y significantly, then

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From the stationary-state equation,

The final rate equation then becomes;

where k2/k-l is very small and can be omitted because k 2 << k-l is required for the first step to be an
equilibrium.

K1 can be measured experimentally in some cases and estimated theoretically in others from
calculation of the electrostatic energy of the interaction, with fair agreement in cases in which both
methods have been used.

Two variations on the interchange mechanism are Id (dissociative interchange) and I, (associative
interchange). The difference between them is in the degree of bond formation in the first step of the
mechanism. If bonding between the incoming ligand and the metal is more important, it is an I,
mechanism. If breaking the bond between the leaving ligand and the metal is more important, it is an
Id mechanism. The distinction between them is subtle and careful experimental design is required to
determine which description fits a given reaction.

As can be seen from these equations, both D and I mechanisms have the same mathematical form for
their rate laws. (If both the numerator and the denominator of the D rate law are divided by k -l/k-l,
the equations have the similar forms shown here.)

At low [Y], the denominator simplifies to [X] for the dissociative and to 1 for the interchange
equation. Both then are second order (first order in M and Y, rate = k[M] o[Y]o or k[M]o[Y]o/[X]), with
the rate of the dissociative reaction slowing as more free X is formed.

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At high [Y], a common condition in kinetic experiments, the second term in the denominator is larger,
[X] + kl[Y] = kl [Y] and 1 + kl [Y]O = kl[Y]O, and [Y] cancels, making the reaction first order in
complex and zero order in Y (rate = (k/k1)[M]o).

The change from one rate law to the other depends on the specific values of the rate constants. The
similarity of the rate laws limits their usefulness in determining the mechanism and requires other
means of distinguishing between different mechanisms.

ASSOCIATION (A)
In an associative reaction, the first step, forming an intermediate with an increased coordination
number, is the rate-determining step. It is followed by a faster reaction in which the leaving ligand is
lost:

The same stationary-state approach used in the other rate laws results in the rate law

This is a second-order equation regardless of the concentration of Y.

Reference texts:

1) Shriver & Atkins: Inorganic Chemistry, 5th Edit. W.H. Freedman & Company, NY., 2010
2) Gary L. Miessler Donald A. Tarr: Inorganic Chemistry, 3rd Edit. Pearson Int. Edition

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