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To the extent that most energy, and all life, on earth derive ultimately from
complexes in solution have been a source of intense study more than five
systems, in particular those involving transition metal complexes did not appear
Chapter 1 Introduction
in the literature until the early 1950s. Perhaps the single, most in-fluential paper
at that time was Henry Taube's classic review [1] in which the substitution
was related to their electronic structures, that is, the foundation for structure-
review [2]. In this review, a direct application of the relationship between rates
of substitution and electronic structure was the study of the reaction between
pathway for electron transfer was clearly defined, and a whole new field of
chemistry, began. Since then, a number of reviews [1-4, 11, 12, 16-80] on
valence molecules [4] and the effect of organic ligands as bridging groups in
electron transfer reactions [5]. Sutin et al. [6-14] has given a good account of
the structural effects on electron transfer [6-8] with special relevance to fi-ee
energy barrier on reactivity pattern [9], role of nuclear fi-equency factor [10, 11],
reactions. Haim et al. [15, 16] has surveyed the mechanism of electron transfer
reactions in terms of the bridged activated states. Sykes et al. [17, 18] indicated
[19, 20] and their relation to structure [21] have been extensively reviewed.
Davies [22-24], Housecroft [25, 26] and Hay [27] made a thorough survey on
vesicle bilayers [29] were studied and have been used as a tool to determine
active centers in proteins [30-34]. Evans [35], Andrieux and coworkers [36]
acceptor systems), and solvent dynamics of charge transfer systems [48, 59, 64].
attention has been given to the evidence of the long-range electron transfer and
the factors governing the rate and direction of the transport [72, 73]. Electron-,
energy- and atom-transfer reaction between DNA and metal complexes has also
[78-80], which transfer its coordinated methyl group as anion, free radical or as
The field of electron transfer has been most active since its beginnings in
1953. During the past several years new avenues of inquiry in the areas of
transfer, radical ion electron transfer, and bioinorganic electron transfer have
reactions are revealed only if one examines the elementary electron transfer
These are the two distinct mechanisms recognized for redox reactions,
which will be outlined in this section and then described in detail in the sections
that follows. The essential difference between these mechanisms lies in the key
(a) +a + o
(b)
Figure 2. The two mechanisms for the transfer of electrons from reductant to oxidant,
(a) The irmer-sphere mechanism, (b) The outer-sphere mechanism.
The earliest reaction of this kind was demonstrated by Henry Taube and
i2+
[Co(NH3)5a]^-^ + [Cr(H20)6]2+ =s^ [(NH3)5CoClCrl 4+
5ir
2+
[Cr(H20)5Cir + [Co(H20)6r^+ 5NH4^
From the appearance of CI" in the inert Cr(III) product, it was deduced
that when electron transfer occurs both metal centers must have been bonded
When the ligands of both reactants are tightly held and there is no change
in the coordination sphere of the two complexes, the reaction proceeds by outer-
Such reactions are those in which both the oxidant and reductant are
iron, chromium and cobalt have been extensively studied [87]. In the case of
Fe^^/Fe^^ reaction, details of mechanism are not available, since both Fe^^ and
D
[Co(NH3)6]^^ (low spin d^) [Co(NH3)6]2+(high spin d')
71 4-Hh4
[Co(NH3)6]2^ (high spin d^) [Co(NH3)6]^^ (low spin d^)
It can be seen that the electron-exchange reaction involves not only the
transfer of an electron but also the rearrangement of the other d electrons of the
two reactants (Figure 3). It is partially spin-forbidden and should proceed very
Basolo and Neuman have proposed [94] that this is the case in the
system, it is probable that only a small amount of energy is required to excite the
spin-paired [Co(H20)6]^^ to the spin-free state; and in the second system, the
excitation energy for the formation of a spin-paired Co(phen)3^"^ from the spin-
free state is probably also small. The field strength for ammonia,
The coordination spheres of the two metal centers remain intact during
[Cr(bipy)3]^^ [95-97]. Reduction reactions [98, 99] involving V(II), Cr(II) and
[Co(NH3)6]^^ systems were also shown to follow outer-sphere path [100, 101].
1. Collision of the donor with the acceptor to form the precursor complex
D+A • [D II A]
[D||A] •[D||A]*
3. Electron transfer
[D||A]^ •[D^llA-]^
[DM|A-]* • D^ + A"
The first step involves the formation of a precursor complex from the reactants.
In the second step, the precursor complex reorganizes itself to form the activated
complex. In the third step, electron transfer takes place during the
principle. The fourth step involves the deactivation of the activated complex
products. In terms of the above scheme, the rate constant, A:obs for the outer-
;tobs=Zpet-«'«^^^J.ef-^°*^^Tl {a)
expCpaAl'-'O expCpaoI'^)
(r) = X exp(-p rl'^O (*)
2Dsr +
l-KPa^l'/O l+(paDl'/0
where, ZD and ZA are the charges on the two reactants, e is the unit of electric
CTD is equal to the radius of the reactant aA and ao, plus the radius of the main ion
dielectric constant of the medium. Equation {b) reduces to the equation (c)
when the distance of closest approach of the metal centers is equal to the sum of
the radii of the reactants [r =CT= (an + aA)] and the radii of all the ions are equal.
Further AG* [in equation (a)] is the minimum free energy increase above the
AG = - ^ 1 +
4 \ X
AG° is the standard free energy of reaction (and equals zero for a self-exchange
Marcus [103] derived an expression for XQ, being the free energy
difference between reactants (D,A) and products (D*, A'), assuming the optical
(Dop) and static (Ds) dielectric constants of the solvent, and the charge
where, ai and a2 are the molecular radii of the reactants and r the intermolecular
separation between them. The expression for the vibrational term A,i is given by
j V + fj
where, f/ andf/ =/** normal mode force constants in the reactants and products
The free energy term, A,o gives the solvent contribution to the energy of
optical transition:
transfer rate constant (ket) and the association constant between reactants (KA) as
follows:
Vet = (2 7uV^/h).(7t/A,RTf^
where, v is the electronic coupling term, and the association constant KA is,
KA = (4 7t NrVsOOO). e ^-<'''>''^'^
AG* has been based on the so-called Marcus cross-relation, which relates the
with the equihbrium constant, K12 = e ("^°*^^'^) of the cross ET reaction, and kn,
is the rate constant of the cross redox reaction for the self-exchange redox
^11
Oxj + redi red, + Oxj
hi2 =(A,i,ii+Xi,22)/2;
A,ii = 4RT (InVetKA)i 1/^11, inserting the expressions for A-n and A,22 to get A,i2, and
incorporating A,i2 into the rate constant, A:obs, the final equation becomes,
W12, W21 are the electrostatic free energy changes associated with the formation
Depending on which step controls the overall rate of reaction, the inner-sphere
Type I: Reactions, in which precursor complexes are readily formed, and the
rate of electron transfer is slow, come under this type (i.e., kp > kgt), Here,
Fe(II) ion. The electron transfer and subsequent Co - CI bond rupture yield
Type II: Due to slow substitution on the reductant, precursor complex formation
is the rate-determining step, and electron transfer takes place immediately after
Type III: In this case, the reactants and successor complex are in equilibrium
and the rate of decay of the successor complex is rate determining step.
ratea[L5M"-X][M'"'L'5]
ratea[L5M"-X-M'"'L'5]
reaction [107]. Movius and Linck reported [108] that the Cr(II) reduction of
alter the rate of electron transfer by changing the interaction energy, the stability
of the precursor complex as well as the standard free energy change for the
bridging ligands and their effects on the electron transfer reaction mechanism.
that forms part of the coordination spheres of both the oxidizing and the
reducing metal ions. The bridging ligand must function as a Lewis base toward
both metal centers; it must have two pairs of electrons that can be donated to
1. When the rate of electron transfer is equal to or slower than the rates of
2. When the rates do not fit with the common tests for an outer-sphere
requirements that the bridging group must have an available lone pair of
reaction partner.
electron pairs available to form a bridge to a second metal ion, but Group 15
atoms (nitrogen, phosphorus, arsenic) have a single lone pair which is fully
essential requirement for inner-sphere electron transfer [109]. Thus, just as CH3
can act as bridge between F and 0H~ in the SN2 base hydrolysis, so it may act as
bridging ligand to be such that electron transmission from one donor site to the
through ligand electron transfer path, then electron transfer must take place by
A ^ X + B - > A + X . B ^ {d)
A \ X + B ^ A . X + B^ {e)
As noted above, other things being equal, the rates of reaction tend to correlate
with the thermodynamic driving force. Thus, if the group X forms a particularly
are observed whatever the bridging group specifically favours B^ rather than A,
It is well known that most metal ions exhibit a marked trend in affinity for
the halide ions [110], and the terms 'hard' and 'soft' have been used [111] to
denote cations which bond preferentially in the order F~ > CI" > Br~ > T and
vice versa. From equation {e), it is clear that for an outer-sphere mechanism, if
the oxidant A^ is 'harder' than the corresponding reduced form A, then rates
with a common reductant B will fall in the sequence I" > Br" > CI" > F".
Most metal ions are indeed 'harder' in the higher valencies than in the lower
[110], and the sequence just mentioned is the one commonly observed [112].
electron transfer process (Scheme 1). Along the unique z-axis, the electron is
transferred from a d^ orbital (a*) on Fe(II) to the c// orbital (CT*) in Co(III)
modified by the presence of the bridge orbital. The energy of the electron donor
orbital is directly related to the strength of the Co-X binding interaction, and so
electron transfer will be strongly coupled to the Co-X strength. Further, the
group trans to the bridge will also have a major effect on the energy of the
orbital. Weakening the Co-trans ligand bond will favour electron transfer.
Strong field ligands raise the energy of the orbital and inhibit electron transfer;
Co-X-Fe
Scheme 1
of halide ions I" > Br" > CI" > F~ for Cr(II) reduction deserves special mention
[86]. The same order is found with [Co(CN)5]^' [114] and may be termed the
'inverted' order, F"> C r > Br~> T is observed. The normal order is found in
the reactions of Cr(II) with [Cr(NH3)5X]^'" [117] or CrX^"^ [118] and the inverted
order when Fe(II) reacts with Co(III) complexes [119]. The bridging efficiency
thus seems to depend primarily upon the nature of the reducing agent and to a
Halpem and Rabani [120] have suggested that for the reactions,
the reactivity order is rightly determined by the strength of the bond being
broken (Co-X) and the bond being formed (X-red). The bond strength in the
present cases increase in the order: Y > Br~ > 01" > F~. For highly reactive
> [Co(NH3)5F]^'". For reductants of low reactivity like Fe(II) [116, 119], bond
transition state of the reactants and hence the reactivity order is influenced by
the strength of the bond being formed, i.e., F" > CI" > Br" > F. The observed
reactivity orders are consistent with this interpretation. Sutin [9], Diebler and
CT-interaction when Cr(II) is used as a reducing agent and for Fe(II) reduction,
bridging the reactants are defined as non-bridging ligands. Since the role of
For the inner-sphere reactions much of the early work on non-bridging effects
was prompted by Orgel's theory [121] and the ready availability of numerous
For inner-sphere reactions in which the d^ orbital accepts the reducing electron,
the theory predicts that the rate of electron transfer is inversely proportional to
the ligand field strength of the group trans to the bridging ligand. Ogard and
orbitals. The first systematic test of these ideas was reported by Benson and
Hahn [122]. They found that the rate of oxidation of Fe(II) by some Co(ni)
Bifano and Linck [123, 127] suggested that the sigma-bonding strength of
a ligand, rather than its position in the spectrochemical series, should be a useful
a series of amines of varying base strength. Although the reduction with Fe(II)
also involved.
be observed even for outer-sphere mechanism, Patel and Endicott [128] studied
sensitivity to the ligation of the Co(III) oxidant [123]. This similarity in the
specific rates of these electron transfer reactions might be factorable into terms
which involve the properties of the oxidizing agent and the reducing agent
sphere);
i.e., ki2 «/n(i) (cobalt):yn(2)(reductant)
Marcus for outer-sphere reactions and this relationship has found some
Hicks, Toppen and Linck [129] reported values for the reduction of
long as the non-bridging ligands are not too rate enhancing. Another interesting
study [130] involves the reduction of superoxide bound to two Co(III) ions by
Fe(II).
4+ 3+
^NH2^ ^NH,^
2+ 3+
Fe + LsCq Col^ •^ Fe + L2Cq C0L2
^0-0^ ^oV
supporting the view that 71-bonded ligands bipy and phen are rate enhancing.
energy and when orbitals of same symmetry are involved in the reaction, the
interaction energy is large. If the ligands have filled or empty 71-orbitals (pTC, d7c.
or 7c-system), those orbitals will interact with the d orbitals of the metal ion
having tag symmetry. The d orbitals of the central metal ion having Cg symmetry
will overlap with the ligand orbitals having a symmetry. Evidently electron
When the Cg reductants, Cr(II) [84, 86] and [Co(CN)5]^" [114] react with
eg oxidants, the reactivity order for X is CI" > N3" » CH3CO2". The Cr(II)
reduction of [Fe(H20)5X]"^ indicates Na" > CI", but they react near the
substitution limit for Cr(II). Fe(II) is thought to react by inner-sphere path and
shows for Cg oxidants, Na" > CI" [116, 131]. The reduction by V(II) of
a matching of the symmetry of metal and ligand orbitals. When the symmetry
of the orbitals of the metal ions that donate and accept the electron are the same,
ligand than azide or acetate. Electron transfer involving a tig orbital would be
overlap of the t2g orbital with the 71 system of azide or acetate. Existing data are
in agreement with these suggestions, but they are insufficient to test the concepts
adequately [15].
The reducing efficiency and mechanism of the reduction depends largely on the
nature of the metal ion reductant and ligands surrounding it. A brief account on
the most well studied reducing metal ions would be pertinent here.
1.8.1. Iron(II)
area of redox studies [134-150]. The redox potential for Fe /Fe couple is
+ 0.74 V [134]. Wada and co-workers have reported the effect of CH3OH [131]
Ohashi and coworkers [136] have reported an increase in rate as the mole
complexes where A is NH3, V2 en, Vabipy, V2 phen, etc., and B is a base have
More positive A V values have been observed for the inner-sphere process.
Davies [146] reported the Fe(II) reduction of Co(III) in both LiC104-HC104 and
NaC104-HC104 mixtures, van Eldik et al. [147, 148] made use of volume of
Fe(II) complexes [147] and Fe(II) [148] as the reductants. The effect of pressure
[149] and the role of distance on intramolecular electron transfer rates between
Co(III) and Fe(II) have also been studied in detail [150]. The thermal and
activation for the thermal process (AV* = 27-37 cm^ mol"') decrease
decrease with an increase in the electrolyte concentration [152]. This trend has
redox reaction.
Ce(IV) as the oxidizing phase, with the reducing phase involving a number of
reductants. The rate of electron transport was controlled by the slower of the
Cr(II) (aq) and Fe(III) (aq) in aqueous HCl phases. The electron transport is
stopped when CI" is replaced by CIO4', owing to the high reduction potential of
anion and X is the halogen ion. Rate constants for both uncatalyzed and base-
catalyzed pathways show an increase in the order CI" < Br" < F. A similar
complexes.
1.8.2. Ruthenium(II)
Ru(II) chemistry is the case with which Ru(II) complexes reduce C104~ to CIO3"
has also been reported [160]. The rates are dependent on the Co(III)/(II)
process.
competes with electron transfer in the reaction with Co(III) cage complexes
[163] for these reactions and it has-been shown that with [Co(en)3] energy
with the electron transfer process. Part of the evidence is that quenching by
[Co(en)3] is faster than with [Co(NH3)6] , the inverse of the order expected if
the electron transfer were the sole mechanism. Electron transfer is the operating
the blue [Co(phen)n]^ ion. This ion reacts in aqueous medium to give a hydride
DNA [175]. The DNA polymer provides an efficient intervening medium for
1.8.3. Chromium(II)
Cr(II) is the most powerful reducing agent of all the available reductants.
J+ .2+ : „ - c O _
Cr'" + e-->Cr"" isE" = - 0 . 4 0 V
there is no [H^]~^ dependence [176]. This has been attributed to the absence of
any basic ligand, which can provide a pair of electron for coordination with the
reductant.
Franco [184] studied the electron transfer kinetics of Cr(II) with tetra-nuclear
isomeric species of Co(III) complexes containing pyridine 2,6-, 3,5-, 2,4- and
path; whereas, the other three isomers reacted by an inner-sphere path with
Candlin et al. [84] compared kinetics data for the reduction of a series of
The variation in rate with V(II) and [Cr(bipy)3] was found to be much smaller
than with Cr(II) and the former two show similarity in variation of the rates and
also [Cr(bipy)3]'^'^ has no free coordination site unlike Cr(II) for substitution,
constant of 93 s'^ in IM HCIO4. Similar observations have been made with the
the intermediate reacts with excess Cr(II) and may be bleached catalytically by
bonded Cr(III) amino acid products in the Cr^^ reduction of N,0-chelated amino
in contrast to an earlier report [187]. The rates are faster than those of
show inverse [H^] dependences and rate constants consistent with an inner-
1.8.4. Vanadium(II)
The reactivity of the reducing agent, V(II) is clearly understood from its
sphere determines the nature of the mechanism. If the rate constant is with in
class [84, 98, 132]. Since V(III) is substitution-labile, product analysis does not
help in predicting the nature of the activated complex and so indirect criteria like
AH* and AS** have to be considered for assigning the mechanism. However,
Hicks et al. [129] reported the V(II) reduction of [Co(NH3)5N3]^'", where in they
0-4-
Several other reactions of V(II) are sufficiently rapid and are unambiguously
1.8.5. Titaniuiii(III)
metal complexes by Ti(III). Fraser and co-workers [197] were the first to use
Ti(III). Birk [199], Bakac and Orhanovic [200] reported the Ti(III) reduction of
azido complexes.
Ti(III) hydrolysis equilibrium. The conjugate base TiOH^"^ reacts faster than the
acid form Ti . Bakac, Marcec and Orhanovic [201] in order to find out a
sphere mechanism, the value of kh being 3.54 x 10' M. Martin and Gould
reductant [204].
[H^]~* terms in the rate law with rates comparable with those found for
and enhanced rates suggest attack by TiOH^^ on the gem-diol hydrated form of
establish the role of bridging oxalate. The reactions are inner sphere and have
rates in the order 0.04 M"' s"*, 10 JVT^ s"^ and 400 M"' s"', respectively, in
correspond to the case where precursor formation is rapid and unfavourable, and
The measured second-order rate constant is then equal to Qpket where Qp is the
equilibrium constant for the formation of the precursor complex and ket is the
rate constant for inter-molecular electron transfer. Under such circumstance, the
role of the bridging ligand is dual [15, 208]. It brings the metal ions together
contribution).
The rate constant for electron transfer between two metal ions may be
energy surfaces of the precursor and successor complexes are functions of the
different sizes and charge distributions and therefore their most stable
corresponds to the crossing of the system from one surface to the other.
The first order surfaces for the system are shown schematically in Figure 4.
The nuclear factor represents the change in nuclear positions, both inner-sphere
that appropriate to the intersection region. At that point, the energies of the
system before and after electron transfer are equal. Whether elecfron transfer
obtains (electronic factor) when the intersection region has been reached
depends on the interaction energy H12. If H12 is sufficiently large (0.5 kcal),
transferred, that is, the system follows the path given by the lower surface.
This process is referred to as adiabatic electron transfer. If H12 is too small, the
system upon reaching the required configuration tends to follow the Hn surface
and only occasionally stays in the lower surface. This process is referred to as
between the metal ions and on the symmetry of the donor, acceptor and carrier
orbitals. Electron transfer between metal centers that use the bridging ligand for
Under some circumstances, the bridging ligand can become involved chemically
in the reaction sequence. The electron (or hole) is transferred to the bridging
finite lifetime. In a subsequent step, the reduced (or oxidized) bridging ligand
transfers the electron (or hole) to the final acceptor and the overall electron
mechanism.
among the most versatile chemicals available. They are amphiphilic molecules
are thus able to interact with both polar and non-polar compounds. Amphiphilic
changing the soap concentration and coined the name micelle for the aggregates.
microemulsions and liquid crystals are included. Micelles are formed over a
fairly narrow concentration range of surfactant and this range is called critical
size is about 3-100 nm and which arise after the attainment of the CMC.
where the surfactant exists. In a specific concentration range above the CMC
which spherical micelles forms [212]. The formation of micelles was often
The CMC can serve as a measure of micelle stability in a given state and the
They have been introduced into several commercial products such as antiseptic
agents in cosmetics and as germicides [213]. They have also found a wide range
research [214] and as catalyst in several organic and inorganic reactions [215].
forces and for a given set of reaction the observed rate depends on the extent of
association between the reactants and micellar aggregates. Most of the chemical
On the otherhand, relatively few works have been carried on the electron
transfer reactions for transition metal ions complexes with lipophilic ligands
[76, 221-227]. We are interested in the synthesis and micelle forming properties
long-time [228-237].
t
o4=o
M"' : Co(III) ^ V '
hydrophobic tail group
hydrophobic tail group
In these surfactants, the metal complex part containing the central metal ion with
its primary coordination sphere acts as the head group and the hydrophobic part
of one or more ligands acts as tail part. Like any other well-known surfactants
concentration (CMC) in aqueous solution [228, 232]. There are but a few
study of such surfactants in solution without isolation. It is argued that the high
charge and size of the head group of the complex having long paraffin tails;
attracted considerable attention as catalyst for the cleavage of esters and amides
there has been increasing interest in the use of these organized media to study