DIRECT ELECTROCHEMICAL

ORGANOMETALLIC COMPOUNDS

SYNTHESIS

OF

INORGANIC

AND

DENNIS G. TUCK
Department of Chemistry and Biochemistry
University of Windsor
Windsor, Ontario N9B 3P4
Canada
ABSTRACT. The method of direct electrochemical synthesis consists of oxidizing a metal anode
in a non-aqueous solution containing a ligand (or ligand precursor) to produce the appropriate
inorganic or organometallic compound. In many cases, the product precipitates directly in the
cell, making for easy isolation, so that the technique is both direct and simple, and in addition
the product yields are very high. One advantage of the technique is that the products are often
derivatives of a low oxidation state of the metal; examples of this include chromium(III) bromide,
tin(lI) and lead(lI) diolates and thiolates, hexahalogenodigallate(lI) anions, thorium diiodide,
copper(l) thiolate complexes, and indium(l) derivatives of thiols, dithiols, and diols. In some
systems, the low oxidation state compound undergoes subsequent reaction; for example, in the
synthesis of RInX2 the reaction sequence involves the oxidation of indium metal to give InX,
which then reacts with RX to give RInX2. Another possible post-electrolysis process is
disproportionation. Examples of these various preparative routes will be discussed.
Details of two recent investigations are also reported. One of these depends on the oxidation
of indium in solutions containing CH2X2 (X = Br ,I), to give X2InCH2X or X2InCX2InX2 species
as the final products. A different system involves the oxidation of indium in liquid ammonia
solutions of NH4X or aromatic 1,2-diols, and the reactions in liquid ammonia are discussed.
1.

Introduction

A basic tenet of many of the papers presented at this meeting is that the electrochemical
technique represents the optimum method of carrying out oxidation or reduction reactions, in
large measure because the removal or addition of electrons to a given solute species can be
achieved without the complications attendant upon the addition of redox reagents to the reaction
mixture. In this paper, we are particularly concerned with preparative electrochemistry, which
is a subject which has developed considerably in recent years in inorganic, organometallic and
biochemistry. The work which we have done in Windsor has concentrated on the use of nonaqueous solvents, and we have been able to prepare a wide range of compounds by the use of
some simple apparatus, and some equally simple ideas. In particular, we are concerned with
electrochemical systems in which the anode serves not only as a sink for electrons but also as a
reagent towards species which are present in solution, or which are generated in solution as the
electrolysis proceeds. The use of a sacrificial electrode is particularly important, because a highpurity metal serves as the starting point of the synthesis. In addition, we have established that
15

A. J. L. Pombeiro and J. A. McCleverty (eds.),

Molecular Electrochemistry of Inorganic, Bioinorganic and OrganomettaJJic Compounds, 15-31.
1993 Kluwer Academic Publishers.

16

the absence of detailed electrochemical parameters such as Eo in preparative non-aqueous

electrochemistry is no more a hindrance to the use of the method than is the absence of
thermodynamic data to the chemist who simply wishes to heat substances together in a flask.
Inorganic chemists were rather slow to recognize the advantages inherent in the use of metals
as reagents, which is surprising given the fact that organozinc halides were first synthesized 130
years ago from Zn + RX, and that the use of magnesium to yield Grignard reagents is
fundamental in organic and organometallic chemistry. The use of high vacuum techniques, which
allow the evaporation of gram quantities of metals into a high temperature vapour, and the
development of the associated equipment for collecting the products, led to a new interest in the
use of metals as synthetic reagents. Our use of metals in direct electrochemical synthesis was
entirely coincidental, but it is worth noting that some of the compounds which we have prepared
have also been obtained by the more exacting methods of vapour phase synthesis. In principle,
one can use the metal as either cathode or anode in direct electrochemical synthesis, but most of
our work has been concerned with anodic oxidation, and the discussion in this paper will be
confined to such experiments. This is not to ignore the many interesting reports on the use of
sacrificial cathodes, some of which have been reviewed elsewhere [1]. I shall also outline the
general directions which our research has taken, and identify the particular ligand systems for
which we believe direct electrochemical synthesis provides advantages of yield and purity .
. The final point to be emphasized is that because one starts with a metal which is by definition
in the zero oxidation state, the experimental technique will necessarily give preferential access
to the lower oxidation states if these can be stabilized in the solvent system in question. In
particular, for a number of metals in the Main Group section of the Periodic Table, direct
electrochemical synthesis is a simple and attractive way of getting to compounds which otherwise
may not easily prepared, and hence provides an entree to the study of their chemistry.
2.

Experimental Outline

As with most electrochemical systems, our work has been conducted at or near room
temperature and with solvent systems which are readily accessible in most laboratories. The cells
which we have used are unsophisticated in the extreme, and the electrical power can be derived
either from a relatively cheap ACIDC rectifier power pack, or in the extreme case from chemical
storage batteries [2]. The typical simple cell shown in Fig. 1 is based on a 100 mL tall-form
beaker; a stream of dry nitrogen passing through the solution allows one to work in oxygen- and
moisture-free conditions. The apparatus can be modified if the products or reagents are very airsensitive, and one such system has been described by Casey et al. [3]. The favoured solvent in
our laboratory is acetonitrile, but other basic solvents, or mixtures thereof, have also been used.
The main criteria are solubility for ligand and background electrolyte, little or no reactivity
towards the product, ease of purification, and stability to an applied voltage of ca. 20 V cm- I .
The background electrolyte has generally been Et4 NCl04 (ca. 50 mg per 50 mL of solution), but
tetraalkylammonium salts of PF6 - or BF4 - have also been used, especially when oxidation by
CI04- is a real or suspected problem.
We normally run experiments at a current of 20-30 rnA, and the applied voltage is then that
required to achieve such a current; typical values would be in the range 10-30 V, depending on
the solutes in the electrolyte phase. The applied voltage required obviously depends on the
electrode potential for the reaction, but more importantly on the EMF needed to drive the current
carriers through a medium of low dielectric constant. Given the use of electrodes with surface
areas of a few cm2 , the current density at the anode is in the order 10-20 rnA cm-2 . These

17

N2 in, out

Pt leads

Figure 1.

Diagrammatic representation of electrochemical cell

MX m-

RMX

RMXL

4-----1

RMX mn

Scheme 1

mMXn

M(NCS)n

18

parameters are by no means unique, but serve as an illustration of the practical conditions which
we have found convenient. The most critical factor is the current, since too low a value gives
only small quantities of product, while a high current density can cause excessive heating of the
cell.
3.

Direct Synthesis of Halides and Related Compounds

The first systematic experiments which we carried out involved the oxidation of metal anodes
in non-aqueous solutions of halogen, especially bromine and iodine. We found that the metal
halides themselves are easily accessible, and that anionic complexes or adducts with neutral
ligands can also be readily prepared by adding the appropriate species to the solution. This work
is summarized in Scheme 1, which shows a range of different syntheses, all of which were
carried out with the simple apparatus described above. An obvious extension was to investigate
the reactions of organic halides, and successful syntheses of RMX, RMX;.-, etc., were found to
be possible, with good yields of product. We were also able to prepare compounds by inserting
a metal into an existing metal-halogen bond, and derivatives of the type Ph3SnZnCl.tmed (tmed
= N,N,N' ,N'-tetramethylethanediamine) were obtained from Ph3SnCI [4].
Another extension is that pseudohalogens can replace halogen, so that neutral and anionic
isothiocyanates are also accessible by this method [5], as are heterometallic carbonyls [6]. A
simple preparation of (ph3PHnCoCI4 makes a useful undergraduate laboratory experiment [2].
All of these processes can be represented as the electrochemically driven oxidative addition of
a metal atom to an X-X, R-X, M'-X or M-M bond. The metals for which such reactions have
been observed in our laboratory in one or all of these systems include Mg, Ti, Zr, Hf, V, Cr,
Mo, Mn, Fe, Co, Ni, Pd, Cu, Ag, Au, Zn, Cd, Hg, Ga, In, Sn, Th and U [7]-[31].
We have not followed this work recently as much as we would have wished, but the range of
experiments, which are discussed in more detail in an earlier paper [1], already shows that both
transition metal and Main Group elements can be used as the anode in such systems, and that a
wide range of useful products can be prepared in a very simple and straightforward way. I do
not propose to discuss this area further, other than to emphasize the particular advantage of such
syntheses, which are that one can prepare the anhydrous halides without resorting to the high
temperature methods which are otherwise required: that removal of water from hydrated
materials is not necessary: that the derivatives (e.g., MX~-, RMX~-, RMXnLm) are as easily
obtained in the one-step synthesis as are the parent halides themselves; and that the products are
obtained in high yield and purity.
4.

Thiolates and Related Compounds

It has been known for many years that thiols or disulfides can be reduced electrochemically to
the corresponding RS- anions. This is the first step in the direct electrochemical synthesis of
metal thiolates and their derivatives, since these anions, or more probably the radicals produced
when the anions discharge at the anode, react with a variety of metals. We have carried out
successful syntheses with the elements Co, Ni, Cu, Ag, Au, Zn, Cd, Hg, In, TI, Sn and Pb to
give M(SR)n' with R = Et, t-Bu, n-Bu, CSH11' Ph, Q-, m-, p-tolyl, 2-naphthyl, etc. (not all
combinations) [32]-[37]. As with the halide systems, one can equally well produce the
compounds themselves, or their derivatives, by appropriate adjustment of the solution phase
conditions. The synthesis of these substances is experimentally simple and straightforward,

19

especially since the products are often insoluble in the solvent systems used, and so can be
conveniently collected beneath the anode.
This is a convenient point at which to introduce the method of chemical accounting which gives
some insight into the mechanism of these and related electrochemical syntheses. For a thiol, the
sequence is
(1)
anode: nRS-

+ M -+ M(SR)n + .!Ie

(2)

giving as the overall stoichiometry

(3)

If a disulfide is used, eq. (1) is replaced by

(la)
and the overall process is
(3a)
There is one noteworthy difference between the two systems, in that none of the metals listed
above react directly with thiols, whereas a number of Main Group metals will undergo a thermal
reaction with Ph2S2 to give reactions which are stoichiometrically equivalent to eq. (3a) [38].
The sum of eqs. (1) + (2), or (la) + (2), corresponds to the obvious fact that electrons flow
through the cell, and leads to an important experimental parameter which we term the
electrochemical efficiency (Ep), defined as moles of metal dissolved from the anode per Faraday
of electricity flowing through the cell. The weight loss at the anode is readily determined; the
total quantity of electricity can be measured either by placing a silver coulometer in series with
the cell and power supply, or by maintaining a constant current by manual control for a given
period of time. Under the typical conditions which we have used, a current of 20 rnA over 2 h
leads to the dissolution of approx. 50-200 mg of metal, depending on the atomic mass of the
latter, so that Ep is easily determined to 0.02 mol F- i . For the elements listed above, the Ep
values are invariably 0.5 mol F- i for Zn, Cd, Sn and Pb, and 1.0 mol F- i for Cu, Ag, In and
Tl. We shall return to a discussion of some of the values below, but for the case of Zn or Cd,
this result is in accord with the formation of M(SRh compounds or their derivatives.
Following the syntheses of thiolato compounds, we also successfully prepared some analogous
M(SePh)n compounds (M = Cu, Ag, Zn, Cd, Tl, Sn) and adducts such as Cd(SePh)z.phen and
CuSePh.1.5Ph 3P by electrolysis with solutions of Ph2Sez in toluene/CH3CN mixtures [39].
Similarly, solutions of Ph2PH in CH 3CN gave M(PPh2)n (M = Co, Cu, Ag, Au, Zn, Cd), and
in an extension of this work, solutions of Ph2PH and S8 in toluene/CH 3CN yielded derivatives
of M(S2PPh2h for Co, Ni, Zn and Cd [40]. These straightforward syntheses lead to studies of
the oxidative and structural investigation of some of these compounds. Attempts to extend the
diphenylphosphido work by using (-C 6H iihPH were not successful, since the products were
extremely unstable.
These syntheses are all characterized by simplicity of procedure, by high yield, and by the
formation of pure products. Since the one-step method requires the use of essentially only metal

20

plus ligand precursor, the chances of contaminating the product are minimized, and we believe
that this approach is an improvement on those in the literature for thiolates and selenolates. The
generality of the methods for phosphido complexes is open to doubt in view of the problems
encountered with {-C6Hl1 }zPH, and further work is obviously required here. The potential
significance of these syntheses lies not only in their simplicity, or in the interesting structures
identified, but also because some of these products may prove to be precursors of the III-V and
IV-VI compounds which are so important in the microelectronics industry.
One interesting and unexpected aspect of these syntheses is that the products of the
electrochemical oxidation of copper included some molecules with unusual cage structure based
on CU4S4' CU2S2' CU4P4' etc., rings [35], [41]-[44]. This is not the place to attempt a discussion
of such structures, nor those of the [M4(SPh)IO]2- anions (M = Zn, Cd), since good reviews have
already been published [45,46], but their easy accessibility by direct electrochemical synthesis
is yet another feature of this versatile method.
Some special mention should also be made of the electrochemical synthesis of amido
complexes. In some early unpublished work, we used solutions of i-Pr2NH, 2,2,6,6tetramethylpiperidine or (M~Si}zNH attempts to prepare M(NR2h compounds (M = Zn, Cd,
Hg), but although solid products were obtained, their properties were not those of the expected
properties, and this work was not pursued in the light of competing interests. With the amine
pY2NH, on the other hand, the experiment proceeded smoothly to give M(NPY2)n (M = Cu, Ag,
Zn, Cd, Tl) [47]. It seems likely that the anions of the amines used earlier, or the radicals
derived from them, react with CH3CN to give species of the type R2NC(CH 3)N-, and that the
products are in fact derivatives of such ligands.
Finally, we may note that if one views the parent ligand precursor (e.g., thiol, phosphine, etc.)
as a weak acid which is reduced cathodically to yield the corresponding anion, then R3CH
compounds can also be included in this group of syntheses. The successful production of
PhCCCu, which is itself a useful synthetic reagent in organic chemistry, from PhCCH (PK - 25)
is one example of this [48], and in related studies of wider implication, Casey [3] and Lehmkuhl
[49,50] have obtained cyclopentadienyl and related compounds. The range of syntheses achieved
with such weak acids, which do not react with metals under non-electrochemical conditions, is
illustrated in Scheme 2.

s.

Bidentate Ligands

A different group of weak acids which lend themselves readily to the direct electrochemical
synthesis of metallic derivatives is illustrated in Scheme 3. These differ from those in Scheme
2 essentially in that the acidic group (OH, SH, etc.) is part of a molecule which contains a second
donor atom, so that cathodic reduction gives an anionic ligand which is a potential chelating
agent. In early studies [51,52], it was found that acac- (2,4-pentandionate) derivatives were
readily accessible by this route, and as in the work described above, the products may be
M(acac)n or M(acac)nLm depending on the solutes present during the electrolysis [53]-[55]. A
number of related bid.entate oxygen donors have been studied, including catecholates [53] and
other aromatic 1,2-diolates [57,58] and carboxylic acids [59]. Bidentate sulphur donor ligands
represent a simple extension of this aspect of direct electrochemical synthesis, and dithiolato [60],
[44], dialkylthiocarbamato [61] and diethyldithiophosphato [61] derivatives have been prepared.
The metals which have been successfully used in this aspect of the work include Cr, Mn, Fe, Co,
Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl' Sn, Th and U.
Once again, it is appropriate to emphasize that the simplicity and directness of the method offer

21

M(SeR)n

Scheme 2

M(acac)n4n

M(acac)n

Hacac. L

M[O(OH)R]n
R(OH)2

~
M(S2 R)n '

M(02 R)n

M[O(OH)R]n

M(S(SH)R]n

Scheme 3

El 3 NH[rn0 2 R]

"3N

In[O(OH)R] ~ 12 In[O(OH)R]

l..Q-02c6~r 4
In[O(OH)R](02 C68r 4)

Scheme 4

22

considerable advantages, both in the procedure itself and in the isolation of pure products. For
example, in the synthesis of metal carboxylates the products are water-free, since aqueous media
are not used, and so do not require extensive washing to remove soluble contaminants. Equally,
in the synthesis of M(acac)n compounds, the direct transformation of metal into complex avoids
dissolution, extraction, etc. as in the more classical approach. Large scale preparations have been
successfully carried out by Lehmkuhl et al. [51].
6.

Strong Acid Systems

Since many metals react directly with aqueous solutions of strong mineral acids, there has been
little incentive to apply electrochemical methods for the preparation of derivatives of these acids.
A brief investigation showed that [Cr(dmso)6]Br3 can be obtained by this one-step route [15], and
later efforts showed that other metals can serve as the starting point for dmso or CH3CN
complexes of the type [ML61(BF4)n for M = V, Cr, Mn, Fe, Co, Ni, Zn, Cd and In [62].
Some work which we were not able to develop fully as would have been wished, using the
heavy elements thorium and uranium, showed that the application of the method is not restricted
to lighter metals, since [Th(dmso)s](N03)4 could be prepared from solutions of nitric acid in trin-butyl phosphate; other media used in this work included N20 4/EtOAc/CH 3CN mixtures [63].
An efficient and compact method of treating spent fuel rods from a nuclear reactor might be
developed around the electrochemical oxidation and dissolution of the metal fuel element.
7.

Low Oxidation State Products

One of the most interesting aspects of the work, as noted earlier, is that low oxidation state
compounds are often produced by the dissolution of a metal anode. A list of some such syntheses
is given in Table 1, and the appropriate papers should be consulted for details. The particular
interest in Main Group metals in our laboratory has again lead us to concentrate on the elements
Ga, In, TI, Sn and Pb, although the early syntheses on copper(l) species [25], of CrBr3 [15], and
of ThI2 [28], show that these are examples of interest in transition and heavy element chemistry.
The contrast between the electrochemical method and the method in the literature is very
striking in one particular case, namely the formation of the tin(lI) compounds by the
electrochemical oxidation of the metal in solutions of 1,2-aromatic diols in acetonitrile (R(OH}z
= catechol, 2,3-dihydroxynaphthalene, Br4C6(OH}z, 2,2'-dihydroxybiphenyl). The room
temperature, high yield, electrochemical synthesis of Sn(OzR) compounds is a great improvement
over the high temperature methods used in the earlier syntheses of such compounds [64]. The
ready accessibility of the Sn(OzR) materials lead to a study of their redox reactions, and their
coordination chemistry. Not surprisingly, the direct synthesis of Pb(OzR), and its redox
chemistry, follow from the tin(ll) system [65]. In each case the Ep value of 0.5 mol F- i can be
understood by the sequence
cathode: R(OH}z + 2e -+ RO~- + H2

(4)

anode: R~- + M -+ M(OzR) + 2e

(5)

giving the overall stoichiometry

23

TABLE 1. Low oxidation state products

Product

Ref.

CrBr3
Ti(acach
CuX
CuSR

15
52
23
35,41-45
28
33

Th~

Sn(SR

Sn(~R)

Pb(02R)

64
65

G~Xl

InX,InI2In(SR)n (n = 1,2)
In[O(OH)R]
In[S(SH)R]
TISR
Tl2~R

27,31
7,67
37
68
69
37
69

TABLE 2. Electrochemical efficiencies (in mol F- 1) for

the oxidation of elemental indium.
Solute

EF

Product

Ref.

RX

-1
1.0 0.1
1.00 0.03

RInX2, etc.
InL3
In(SR)n
n = 1,2,3
In(SePhh(?)
no stable product
In[O(OH)R]
In[S(SH)R]
In(02Rh
no stable product
X2InCH2X, etc.

20
61
37

~NCSm

RSH

Ph2S~

PY2NH
R(OH)2
R(SH
R(O)OH
Ph2PH
CH2X2

1.00
1.10
1.01
1.00
1.02
1.05
1.02

0.01

0.03

0.01

39
47
68
69
57,58
40
67

24

R(OHh + M .... M(~R) + H2

(6)

As with the cases discussed above, this reaction does not occur under normal conditions. We
also found that with the aromatic thiols (RSH); the primary products were Sn(SRh or Pb(SRh,
although subsequent (unidentified) oxidation processes in the presence of bidentate donors gave
Sn(SR)4.bpy etc. for tin, despite the fact that the Ep of 0.5 mol F- 1 showed that the
electrochemical processes are essentially unchanged by these donors from eqs. (1) + (2) [33].
The results with the elements gallium, indium and thallium are particularly interesting in this
context. With thallium + RSH or R(SHb as with other ligands, the products are invariably
those of thallium(I), and Ep = 1.0 mol F- 1 [37], which is in keeping with the known stability of
this oxidation state; in the case of solutions of R(OHh, the product is contaminated with thallium
metal formed by cathodic reduction of the slightly soluble product [66]. With gallium, one can
obtain either the Gll:J.xi- anionic complexes of gailium(Il) from solutions containing HX (X =
Cl, Br, I), with Ep - 0.6, or GaX4- from solutions of X- + X2, although the Ep values show
that a gailium(Il) species is again formed at the anode, with subsequent oxidation to gallium(III)
in the electrolyte phase [27].
Indium yields indium(lIl) compounds as the products in a number of cases, but the Ep value
of 1.0 indicates clearly that the product of anodic oxidation is an indium(l) species. (See Table
2.) Some special cases are worth discussing. In the oxidation of this element in solutions of RX
(R = Me, Et, Ph, Bz, C6FS; X = CI, Br, I; not all combinations) the isolated products are
RInX2, RInX2.bpy or ~N[RInX3] depending on the composition of the electrolyte, but in every
instance one finds Ep = 1.0 mol F- 1, implying the sequence
cathode: RX + e .... R + X-

(7)

anode: X- + In .... InX + e

(8)

followed by oxidative insertion and complexation

InX + RX .... RInX2

(9)
(10)

Similarly, solutions of CH2X2/CH 3CN (X = CI, Br, I) give Ep = 1.0 mol F- 1, and in the case
of X = Br or I, the products are derivatives of ~InCH2X; InCI disproportionates in these
systems to give In 0 + InX3. The oxidative reactions of InX have been sufficiently well studied
in non-electrochemical work for the chemical processes (9) and (10), and the disproportionation,
to be well understood [67].
A similar situation has been found in attempts to synthesize indium complexes of a number of
the ligands identified in Schemes 3 and 4. With solutions of bidentate oxygen donors [57,58],
or ~NCSH [61], Ep = 1.0 mol F- 1, but in each case the product recovered from the reaction
mixture is InL3, while for Ph2PH or pY2NH but the presumed InL species is too reactive to allow
any identifiable product to be isolated. These results suggest that there are again post-electrolytic
oxidative processes, possibly of the type

+ HL .... H~

(11)

HI~""H + hi~

(12)

InL

hi~

.
+ HL .... H +

25
I~

(13)

2hi~ .... I~L4

(14)

2H + 2InL .... 2HL + 2In

(15)

Research into such reactions, in which one-electron transfer is the essence of the presumed
mechanism, is planned. The only conclusion possible at the moment is that indium(l) species are
the favoured product of the anodic oxidation of this element. One system in which InL, ~L4
and InL3 species were identified was for L = SR, where the nature of R appears to have a strong
influence on the sequence of reactions such as eqs. (11)-(15) [37].
Finally, we note the unusual compounds prepared from indium and solutions of aromatic 1,2diols [68] or aliphatic dithiols [69], where the interest is on both the low oxidation state of the
metal and the structure of the ligand. In each system, the product is an indium(I) complexes of
the type In[O(OH)R] or In[S(SH)R] in which only one of the two acidic hydrogens of the parent
has been lost. The electrochemical efficiency is unity, which can be explained in at least two
ways. In the first of these, the sequence eq. (4) + (5) (see above) is followed by
Inz(OZR)

+ R(OH}z .... 2In[O(OH)R]

(16)

with an overall stoichiometry analogous to eq. (6), namely

R(OH)z + In .... In[O(OH)R] + IhHz

(17)

and as before it should be noted that this reaction only occurs in the electrochemical cell.
An alternative to eqs. (16)-(18) is to replace eq. (4) by
cathode: R(OH)z + e .... R(OH)O- + IhHz

(18)

and the anode process is then obviously

R(OH)O- + In .... In[O(OH)R]

(19)

This would entail a revision of eq. (5) to allow for a sequence such as
solution: R(OH)O- + R(OH)z .... [R(OH)O(OH)zRr

(20)

anode: 2[R(OH)O(OH)zRr + M .... M(OzR) + 2e + 3R(OH)z

(21)

and a number of other variants can also be invented. There is no experimental evidence as to
the species in solution, but since the existence of the products is unquestionable, further work on
this matter is indicated.
The chemistry of these species involves two types of reaction, namely removal of the hydrogen
to give (e.g.) Et3NH+[InOzRr and the oxidation to the corresponding indium(Ill) species by
iodine or Q-quinone. These are summarized in Scheme 4. We have not been able to obtain
crystals of either In[O(OH)R] or In[S(SH)R] compounds, but fortunately a related thallium(l)
compound, Tlz[O(OH)C 1ZHs1z, was prepared many years ago [70], and this has a dimeric
structure based on a TlzOz ring with a lone pair of electrons on thallium(l) [66]. Generally, the

26

chemistry of In[O(OH)R] and In[S(SH)R] compounds can be satisfactorily explained on the basis
of an analogous structure, especially since compounds with In2~ rings have been identified in
other studies. There is still much to be done to develop the chemistry of indium(l), and direct
electrochemical synthesis hllS provided a most useful entry in a new aspect of this work.
The structure of the singly protonated ligand, as well as the nature of the species generated the
electrolyte phase, is another challenging aspect of this work. The indium(l) compounds are not
unique in this respect, since studies with copper anodes and solutions of aromatic 1,2-diols gave
a copper(l) derivative ofR(OH)O- as the adduct C~[OC6CI4(OH)h.diphos [71]. Further work
involving other metals and such ligands is planned.
8.

Solutions in Liquid Ammonia

We have not attempted to carry out any direct electrochemical syntheses in aqueous media, but
there are reports in the literature of work carried out some 40 years ago on the electrochemical
oxidation of a number of metals in liquid ammonia [72,73], and since two of the metals in
question were gallium and indium, this seemed a natural area for further investigation. The
immediate conclusion, which we established by measuring !!p, is that indium is oxidized in liquid
ammonia solutions of ammonium halides at -35C to the +II state, but unfortunately we were
not able to isolate any compounds of this oxidation state from the resultant solution, although in
one particular case we were able to show by Raman spectroscopy that species with the
characteristic p(ln-In) stretching mode were present in the solution [74]. When we attempted to
work up these solutions both indium (I) and (III) halide derivatives of ammonia were obtained,
and a mass balance, taking into account the quantity of material isolated and the quantity of
indium dissolved, showed that the typical disproportionation reactions of indium +II were indeed
being reproduced under these conditions. We concluded that the overall stoichiometry is
(24)
but that unfortunately the inherent instability of I~X4 in these solutions, even in the presence of
ligands known to stabilize these species in other circumstances, means that this is not a useful
preparative route to indium(Il) complexes.
We also investigated solutions of quinones and substituted catechols, in the latter case using
mixtures of ammonia and an organic solvent to achieve sufficient solubility, and here the
electrochemical efficiency shows that indium goes to the +III oxidation state. In the presence
of an Q-quinone, oxidation of the lower oxidation state halide leads to InX(catecholate), and hence
by substitution to InX3 When a 1,2-diol is used, there are again questions as to the solute
species which are generated at the cathode, but the overall reaction can be written as
(25)
with Ep = 0.33 mol p-l. The indium(III) derivative of 3,5-di-tert-butyl-catechol is in fact the
dimeric anion [In2(dbcatechoIMNH3)4]2-, whose crystal structure confirms the presence of the
substituted catecholate ligand, and shows that the dimer is dependent upon an In2~ ring.
It seems likely that the use of liquid ammonia media may offer some advantages in the direct
electrochemical synthesis of low oxidation state complexes. We hope to investigate this matter
in the future.

27

9.

Conclusions

I have tried to show that the use of a metal as the sacrificial anode in electrochemical
oxidation can form the basis of a very wide range of syntheses of inorganic and organometallic
compounds. We believe that the method is indeed a choice one for a series of ligands derived
from weak mono- and dibasic organic acids, and that while we have not investigated all metals
ourselves, there seems every reason to assume that the range of syntheses could be extended to
most areas of the Periodic Table.
The emphasis in our work on the metallic elements Zn, Cd, Hg, Ga, In, TI, Sn and Pb is
a logical consequence of the synergistic effect of other work going on in our laboratory. These
electropositive metals do not generally react with weak organic acids, but the driving force
provided by the applied potential brings about reactions which proceed with an understandable
stoichiometry, with high yield, and under mild conditions. I believe the range of syntheses
discussed in this paper has served to establish direct electrochemical synthesis as a useful and
readily accessible experimental technique for those who are not afraid to use electricity in
chemistry.

10. Acknowledgement
Much of the work reported in this and other papers has been supported by Operating Grants
from the Natural Sciences and Engineering Research Council of Canada. It is also a pleasure to
acknowledge my gratitude to the large number of co-workers whose names are recorded in the
papers which I have quoted here and elsewhere.

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