The Direct Electrochemical Synthesis of ( (C6H5) 3Ph) 2 (CoCl4)
The Direct Electrochemical Synthesis of ( (C6H5) 3Ph) 2 (CoCl4)
The Direct Electrochemical Synthesis of ( (C6H5) 3Ph) 2 (CoCl4)
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
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.
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.
~~
~~
(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)
~~
* CoCL2-
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