Electron-transfer processes

The simplest redox reactions involve only the transfer of electrons, and can be monitored by using
isotopic tracers, e.g. reaction 25.46

If [KMnO4] is mixed with unlabelled [KMnO4]2-, it is found that however rapidly [KMnO 4]2- is precipitated
as BaMnO4, incorporation of the label has occurred. In the case of electron transfer between [Os(bpy) 3]2+
and [Os(bpy)3]3+, the rate of electron transfer can be measured by studying the loss of optical activity
(reaction 25.47).

Electron-transfer processes fall into two classes, defined by Taube: outer-sphere and inner-sphere
mechanisms.

In an outer-sphere mechanism, electron transfer occurs without a covalent linkage being formed
between the reactants. In an inner-sphere mechanism, electron transfer occurs via a covalently bound
bridging ligand.

In some cases, kinetic data readily distinguish between outer- and inner-sphere mechanisms, but in
many reactions, rationalizing the data in terms of a mechanism is not straightforward.

Inner-sphere mechanism

In 1953, Taube (who received the Nobel Prize for Chemistry in 1983) made the classic demonstration of
an inner-sphere reaction on a skilfully chosen system (reaction 25.48) in which the reduced forms were
substitutionally labile and the oxidized forms were substitutionally inert.

All the Cr(III) produced was in the form of [Cr(H 2O)5Cl]2+, and tracer experiments in the presence of
excess, unlabelled Cl- showed that all the chloro ligand in [Cr(H 2O)5Cl]2+ originated from [Co(NH3)5Cl]2+.
Since the Co centre could not have lost Cl - before reduction, and Cr could not have gained Cl - after
oxidation, the transferred Cl- must have been bonded to both metal centres during the reaction.
Intermediate 25.3 is consistent with these observations.

In the above example, Cl- is transferred between metal centres; such transfer is often (but not
necessarily) observed. In the reaction between [Fe(CN) 6]3- and [Co(CN)5]3-, the intermediate 25.4 (which
is stable enough to be precipitated as the Ba 2+ salt) is slowly hydrolysed to [Fe(CN)6]4- and
[Co(CN)5(H2O)]2- without transfer of the bridging ligand. Common bridging ligands in inner-sphere
mechanisms include halides, [OH]-, [CN]-, [NCS]-, pyrazine (25.5) and 4,4’-bipyridine (25.6); pyrazine acts
as an electron-transfer bridge in the Creutz–Taube cation and related species (see structure 22.57 and
discussion).
The steps of an inner-sphere mechanism are bridge formation, electron transfer and bridge cleavage.

Equations 25.49–25.51 illustrate the inner-sphere mechanism for reaction 25.48; the product Equations
25.49–25.51 illustrate the inner-sphere mechanism for reaction 25.48; the product [Co(CN) 5]2+ adds H2O
and then hydrolyses in a fast step to give adds H 2O and then hydrolyses in a fast step to give [Co(H 2O)6]2+.

Most inner-sphere processes exhibit second order kinetics overall, and interpreting the data is seldom
simple. Any one of bridge formation, electron transfer or bridge cleavage can be rate determining. In the
reaction between [Fe(CN)6]3- and [Co(CN)5]3-, the rate-determining step is the breaking of the bridge, but
it is common for the electron transfer to be the rate-determining step. For bridge forma-tion to be rate
determining, the substitution required to form the bridge must be slower than electron transfer. This is
not so in reaction 25.49: substitution in [Cr(H 2O)6]2+ (high-spin d4 ) is very rapid, and the rate-determining
step is electron transfer. However, if [Cr(H 2O)6]2+ is replaced By [V(H2O)6]2+ (d3 ), then the rate constant
for reduction is similar to that for water exchange. This is also true for the reactions between [V(H 2O)6]2+
and [Co(NH3)5Br]3- or [Co(CN)5(N3)]3-, indicating that the bridging group has little effect on the rate and
that the rate-determining step is the ligand substitution required for bridge formation (the rate
depending on the leaving group, H2O)

CHEMICAL AND THEORETICAL BACKGROUND

Box 25.2 Timescales of experimental techniques for studying electron-transfer reactions

In Section 2.11, we discussed fluxional processes in relation to the timescales of NMR and IR
spectroscopies. A range of techniques are now available to probe electron-transfer reactions, and the
recent development of femtosecond (fs) and picosecond (ps) flash photolysis methods now allow
investigations of extremely rapid reactions. For his studies of transition states of chemical reactions
using femtosecond spectroscopy, Ahmed H. Zewail was awarded the 1999 Nobel Prize for Chemistry.

For reaction 25.52 with a range of ligands X, the ratedetermining step is electron transfer, and the rates
of reaction depend on X (Table 25.8). The increase in k along the series F -, Cl-, Br-, I- correlates with
increased ability of the halide to act as a bridge; k for [OH]- is similar to that for Br-, but for H2O, k is very
small and is also pH-dependent. This observation is consistent with H 2O not being the bridging species at
all, but rather [OH]-, its availability in solution varying with pH.

Thiocyanate can coordinate through either the N- or S-donor, and the reaction of [Co(NH 3)5(NCS-S)]2+
(25.7) with [Cr(H2O)5]2+ leads to the linkage isomers [Cr(H2O)5(NCS-N)]2+ (70%) and [Cr(H2O)5(NCS-N)]2+
(30%). The results are explained in terms of different bridge structures. If the free N-donor in 25.7 bonds
to the Cr(II) centre to give bridge 25.8, then the reaction proceeds to form [Cr(H 2O)5(NCS-N)]2+.
Alternatively, bridge structure 25.9 gives the green [Cr(H 2O)5(NCS-N)]2+; this is unstable and isomerizes to
the purple [Cr(H2O)5(NCS-N)]2+.

Conjugated organic anions (e.g. ox2-) lead to faster inner-sphere reactions than non-conjugated anions
(e.g. succinate, -O2CCH2CH2CO2). In the reaction of [Fe(CN)5(H2O)]3- with [Fe(NH3)5(25.10)]3+ in which the
spacer X in 25.10 is varied, the reaction is fast when X provides a conjugated bridge allowing efficient
electron transfer, and is slower for short, saturated bridges such as CH 2. However, rapid electron
transfer is also observed when the spacer is very flexible, even when it is a saturated (insulating) chain.
This observation is consistent with the metal centres being.

brought in closer contact and a change to an outer-sphere mechanism.