PROTOCOLE 410

The Direct Electrochemical Synthesis of

An Example of the Use of Anodic Oxidation in the Preparation of Metal Ion Complexes
Colln Oldham1 and Dennls G. Tuck2
University of Windsor, Windsor. Ontario, Canada N9B 3P4

Althoueh electrochemistrv is an imnortant Dart of undergraduate lecture courses, experiments designed to familiarize
students with this area of chemistrv are freauentlv absent
from the associated laboratory. 1; general; much of the
teaching of electrochemistry, particularly in introductory
courses, concentrates on the equilibrium aspects of the
subject, which are conveniently related through electrode
potentials to elementary thermodynamics. The student may
then he unaware of the many applications of electrochemistry
in the laboratory and on the industrial scale, and topics such
as electrodeposition, electrowinning, and electrochemical
refining often receive only passing mention.
Another neglected topic is the use of electrochemistry in
svnthesis. which is unfortunate since the electrochemical
technique is one of the sunplest and must direct methodsof
achieving oxidation or reduction. Electrons can he removed
from or added LO a system without the complications often
otherwise associated with the presenre of redox reagents, and
there are several useful examples of rhe use of electrochemiral
oxidnrion or reduction in organic iynthesis. The numher of
analognus experiments involving the preparation uf inorganic
or organometallic compounds is more limited, despite the
large amount of information a\.ailat~lefrom physiro-chemical
studies of the hehavior of inurganir and organometullic species
at electrodes (1.2).One ohviuus diftirulrv is that exneriments
in aqueous solution may result in hydrolysis rea'etions involving either starting materials or nroducts.
In addition to those electrochemkal syntheses which involve inert electrodes, there are svstems in which one or both
of the electrodes serve not o n l i a s a source of, or sink for,
electrons, but also u n d e r ~ oreaction with species mesent in
solution, or grnerated in solution as the t~lrcirolysisproreeds.
Such reactions are said to inwlve sacrificial electn~des,and
the metal electrode may now serve as the starting point of a
synthesis. This is important, since there has been much in-

420

Journal of Chemical Education

A~art
terest in recent vears in the use of metals as reazents.
"
from classical examples like the Grigard reaction, recent experiments in which the vaporization of a metal is followed by
reaction with a suitable ligand have considerably extended
the svnthetic a ~ ~ l i c a t i oofnelemental metals (3.4). In reneral
such-vapor
syntheses involve fairly c&n&icatkd apparatus, whereas the electrochemical oxidation or reduction
bf a metal generally can be carried out a t room temperature
with unsophisticated equipment. A variety of inorganic and
organometallic compounds have now heen prepared by this
method ( 5 ) ,and the suggested industrial applications include
the manufacture of tetraethyl lead directly from the metal.
The present experiment presents a simple method for the
direct synthesis of a phosphonium salt ofthe tetrachloroco- . source of electrical energy is a
haltate(I1) ion, C O C I ~ ~The
readilv available 6 V lantern hatterv.
" Anart
. from this. the
apparatus required is that generally available in undergraduate laboratories. The cohalt metal, which serves as the anode
of a cell, is oxidized in situ, thus allowing the student to observe that electrical energy derived from the chemical reactions in a dry cell can he used to drive other reactions, in this
case the synthesis of a transition metal complex. The salt
which is ~ r o d u c e dhas some interestina features. since the
cation is the unusual triphenylphosphGnium species, which
mav be studied hv vibrational s~ectrosconv.and the anion is
a ciassical tetrahedral cobalt ~ I I )speciks.'The electrolyte
phase in the cell consists of acetonitrile containing triphenylphosphine and a few milliliters of concentrated aqueous

' Permanent address: Depanment of Chemislry, University of Lancaster. Lancaster, England Saooatcal leave from the Un'vers ty of
Lancaster and a travel grant from the MinnaJames-Heineman-Stiflung
of Hanover are both gratefully acknowledged.
Author to whom correspondence should be addressed.

PROTOCOLE 410
a i t h dirrhyl ether to remove any triphrnylphosphine. The cobalt
anudr i, washed wlth acetonitrile, dried, and weighed, so that the
quantity of metal diisulvtd ran be determined.

hydrochloric acid. Recently, we

h'sve shown that solutions of
similar composition find general application in the preparation of anionic complexes of
transition and main group
metals (6).One particular advantage is that the presence of
the hydrochloric acid results in
a high conductivity, which in
its turn allows the use of a
cheap low voltage battery.

Results and Discussion

I n a typical experiment, 70 mg of cobalt (1.2 mmol) was
removed from the anode, and 0.8 g of product (1.1mmol) was
isolated. Yields of 9070, based on weight of metal dissolved,
have been obtained routinelv hv this orocedure.
The current efficiency (EF~,defined the number of moles
of metal dissolved per Faradav of electricitv passed, aives
valuable information on the oxidation
it the anode.
The weight loss gives the moles of cohalt dissolved, and the
number of Faradays is given by It/F (I = constant current, in
A; t = time of electrolysis, in sec; F = Faraday constant =
96480 Coulomb). With the apparatus and conditions specified,
EF is 0.50 f 0.01 mol F-l; in our experience, any significant
deviation from this value is usually the result of current
variation during the electrolysis. The value of EFimplies that
the overall stoichiometry of anode process is

as

Procedure
Apparatus
The electrical power is supplied
by a6VLanterndry battery (e.g.,
EverReadP No. 731). A simple
voltmeterlammeter is the only
other piece of equipment required.
The experiment is most simply
performed in a 100-mL tall-form
beaker fitted with a rubber stopper
through which are inserted electrical leads to the electrodes, and
two glass tubes. One tube serves to
permit escape of hydrogen gas
generated at the cathode, and this Simple cell for electrochemical
arrangementallows input and exit synthesis of [(CBH&PH]~[COCIII
of nitrogen gas should one wish to and related experiments.
do experiments in an inert atmowhere. The leads need to be
chemically resistant and mechanically strong, and 1mm diam. platinum wire is adequate,although some saving can be effectedby using
a cohalt rodanode inserted into the cell through
- the rubber stopper.
..
A ewnd plarinum wire, mod usrfully wmnd mlo a mmll rcd, serves
as the cathude of the cell. Other and more elalrmatr rrll- ran be used
at the CUSI of losmg the rimpliriry nnd nhusinrss of the arrangemen1
shown in Figure 1.
~~

which is followed by formation of the complex

CoClz + 2c1-

+ Cl(C6Hd3P+ HCI = (CGHE)~PH+

The weighed cobalt foil suspended on a platinum wire lead forms

the anode of the cell; a small hole drilled through the foil makes for
easy operation. The solution phase can be made up directly into the
100-mL beaker, and the rubber stopper carrying the electrodes and
gas inputleait tubes fitted in place. With the conditions described,
completion of the electrical circuit typically gives a current of 35-50
mA for an applied voltage of 5 V. The time at which the circuit is
closed should be noted. As the electrochemical reactions proceed,
hydrogen gas is evolved at the cathode, and a deep blue coloration
forms at, and streams away from, the cobalt anode. The current should
be read from time to time during the electrolysis to ensure that a
constant value is being maintained,since such constancy is assumed
in the calculation of the current efficiency.
It is convenient to run the electrochemicaloxidation for ~ 9 min.,
0
corres~ondineto the Dassaee of ~ 2 4 Coulomb.
0
The time at which
the c e i is disconnectei shouid he noted. The cell then contains a deeo
Irlur solutim, indi~alingthe iormarion in sin, ot'rhe O,CllL- nnim.
Thr solvent ran he conwnicnrly removed in vacuo, when the crystnllme depp blue [~CsHsrcPlI]r[C~~C14]
prerplrnres; thu is wnrhed
~

~~

(3)

Extenslons
The triphenylphosphonium cation has been the subject of
a number of preparative and spectroscopic investigations. A
recent paper (6) in which an X-ray determination of the
structure was reoorted also noted some imoortant asoects of
the vibrational specrrum; "(P-H, at 2360 & - I is difiicult to
h e w e in the infrared, but it is readily detected in the Raman
spertrum, and t w P-H bending modes are observed at 1112
and 722 c m - ' in the infrared (KHr disc). The paramagnetic
tetrachlorocobalute(111 anion is n well-characterized example
ot a tetrahrdriil~l-rvmplex 17), and can serve as the focal point
of discussion of electronic spectroscopy and structure: The
compound is air-stable, a t least over some hours, and soluble
in acetonitrile, so that spectral and other information can be
obtained easily.
Two other interestine discussion noints involve a cornoarison of the chemical an2 electroche&ical reactions of m&ls
with acid, and the effect of prolonged electrolysis which
eventually favors the formation of the neutral adduct
[(C6H5)3P]&C12 by depleting the hydrogen ion concentration. Experimental variations of metal or mineral acid offer
challenges for the thoughtful student.

Experimental Conditions
Requirements: a strip of cobalt, --3 X 1X 0.1 em
30 mL acetonitrile (Reaeent made)
2 mL cone. aqueous hydrochloric acid
0.5 g triphenylphosphine

~~

(2)

and of course hydrogen evolution a t the cathode is the result

of the discharge of hydrogen ions.

~~

* CoCL2-

T h e triphenylphosphonium cation is obviously formed by

Literature Cited
ill
. . Lehmkuhl. H . . " h i c El&x&emistrv."
.. M. M. Bsizer IEdiforI.
.
.. MareolIkkkar.. N.Y..
1973. p i . 6214%
(2) Settineri, W
. I. and McKeeuer. L. D. "Technique af ElenrmrganicSynfheaia," N. L.
Weinberg (Editor) Wilay~Interseirnee,New York, PeriI1,1915,pp. 397598.
(3) Timms. P. L., Ad". lnorg Radioehem., 14.121 11972).
(4) Ozin, G. A, and Van der Vort, A.. Prog Inorg. Chem.. l9.105 (19'75).
15) Tuck, D. G..PVreAppl. Chem..5l,ZW511979l.
(61 Khan. M., Oidham. C., Taylor. M. Land Tuck, D. G., lnorg.Nucl. Chem. Lett., 16,469

il9Mi

(7) Cotton. F.A. and Wilkimn, G., "Advaneod Inolgsnie Chemistry: Wiley-lntemicna.
New York, 3rd Ed., pp. 880-882.

Volume 59

Number 5

May 1982

421