J. Electroanal. Chem.

, 163 (1984) 415--418 415

Elsevier Sequoia S.A., Lausanne -- Printed in The Netherlands
Preliminary not e
ELECTROREDUCTI ON OF SELENI UM AT A MERCURY POOL CATHODE
IN APROTI C MEDI A
APPLI CATI ON TO THE ELECTROSYNTHESI S OF DI BENZYL SELENI DE
AND DI SELENI DE
B. GAUTHERON and C. DEGRAND*
Laborat oi re de Synt h~s e et d' El ect rosynt h~se Organomdt al l i ques assocl~ au C. N. R. S.
( L. A. 33), Facul t d des Sci ences, 6 bd Gabriel, 21100 Di j on (France)
(Received 2nd February 1984)
INTRODUCTION
In t he l ast t wo decades, i t has been s hown t hat or ganosel eni um c ompounds
are i mpor t ant reagent s and i nt er medi at es in organi c synt heses [1, 2] . Most of
t hese c ompounds cont ai n a C--Se bond and a f ew of t hem a met al - - Se bond
[3, 4] . The st art i ng mat eri al s f or t hei r pr epar at i on i ncl ude sel eni des, R2Se, and
di sel eni de deri vat i ves, R2Se2. Most s ynt het i c met hods pr esent di sadvant ages
[5, 6] . A r ecent me t hod is t he one-fl ask synt hesi s of di al kyl sel eni des and di-
sel eni des by t r i al kyl bor ohydr i de r educt i on of sel eni um [ 5] . However , t he com-
merci al l y available hydr i des r emai n expensi ve. A me t h o d f or t he el ect r ochem-
ical pr epar at i on of al kyl and aryl di sel eni des has r ecent l y been descr i bed [6, 7] .
A Se el ect r ode consi st i ng of a mi xt ur e of Se and graphi t e f used upon a Pt net
was cat hodi cal l y pol ar i zed in DMF cont ai ni ng an al kyl or aryl halide.
The pur pos e of t hi s s t udy was t o s how t hat Se powde r can be r educed t o
pol ysel eni de ani ons and fi nal l y t o Se 2- on a mer cur y pool cat hode in apr ot i c
medi a. In sol vent s such as N, N- di met hyl f or mami de ( DMF) and acet oni t r i l e
(MeCN), di benzyl sel eni de was obt ai ned wi t h high cur r ent effi ci enci es ( > 86%)
when t he el ect r ol yses wer e carri ed out in t he pr esence of benzyl chl ori de.
EXPERIMENTAL
An Amel 552 pot ent i os t at and a Tacussel IG5-N wer e used f or t he pr epar at i ve
el ect r ol yses. The vol t ammet r i c exper i ment s wer e carri ed out wi t h a Tacussel
UAP 4 uni t and a GSTP f unct i on generat or. The i--E curves wer e r ecor ded on
an Ifel ec 2025 C X- - Y r ecor der . A hangi ng mer cur y dr op el ect r ode (HlV!_DE)
was pr epar ed t o t he pr ocedur e descr i bed in ref. 8. Acet oni t r i l e and DNIF of
anal yt i cal grade wer e careful l y dr i ed t hr ough a col umn of neut r al al umi na.
Tet r ahydr of ur an ( THF) was di st i l l ed pri or t o its use.
*To whom correspondence should be addressed.
0022-0728/84/$03. 00 1984 Elsevier Sequoia S.A.
416
General electrolysis procedure
The three compart ment s of an H-type cell were filled with dry solvent con-
taining Bu4NPF6 (0.1 M) as the supporting electrolyte. The cat hode was a
stirred mercury pool (area = 13 cm 2) and t he anode a Pt grid. The potentials
were measured vs. a saturated calomel electrode (SCE) and mai nt ai ned at -1. 1
or - 1. 2 V during t he electrolysis. The cat hol yt e (60 ml) was deaerated with
argon; it cont ai ned selenium (158 mg, 2 10 -3 mol) in its powdered dark gray
form (Merck). Benzyl chloride (0.5 ml, 4.3 X 10 -3 mol) was added before or
after electrolysis. Selenium reduct i on was onl y partially carried out. Selenium
powder which remained black when benzyl chloride was present during elec-
trolysis t ended to stick to t he walls of t he cathodic compart ment s. After elec-
trolysis, t he cat hol yt e was diluted with water and ext ract ed with di et hyl ether.
The solution was dried and t he solvent removed under vacuum. The NMR spec-
t rum of t he residue which still cont ai ned some benzyl chloride was recorded.
From t he integrated curve of t he 1H NMR spectrum, t he amount of electrogen-
erated dibenzyl selenide (I) [9] and diselenide (II) [9] was determined. Diben-
zyl selenide and diselenide were purified by t hi n layer chromat ography (TLC).
I lI
RESULTS
Although no cathodic peak was observed in DMF, by vol t ammet ry at a sta-
t i onary or rot at i ng electrode (HMDE or glassy carbon electrode), t he electro-
reduct i on of Se on a mercury pool cat hode occurred at - 1. 1 V and proceeded
smoot hl y; t he faradaic current did not exceed 20 mA whatever t he rat e of
stirring. A red coloration of the cat hol yt e occurred; it t urned brown as t he elec-
trolysis proceeded. After t he consumpt i on of 0.97 10 -3 moles of electrons,
t he electrolysis was stopped and benzyl chloride added. The cat hol yt e became
red again. When it was diluted with water, colloidal dark red selenium precip-
i t at ed which became gray on standing. A mi xt ure of I and II was isolated (ent ry
1 of Table 1). When t he experi ment was carried out in t he presence of benzyl
chloride (entry 2 of Table 1), an increase in the faradaic current up t o 44 mA
was observed as the electrolysis proceeded and dibenzyl selenide was t he mai n
compound isolated.
In MeCN, dibenzyl selenide was quantitatively isolated when t he applied po-
tential was - 1. 2 V and when benzyl chloride was present during t he electrolysis
(entry 3 of Table 1). The faradaic current did not exceed 10 mA in MeCN and
in THF where a low yield of I was obt ai ned (entry 4 of Table 1).
Both selenide derivatives, I and II, are electroactive. The repetitive cyclic vol-
t ammogram of II in DMF at a HMDE is shown in Fig. 1. A reversible peak sys-
t em is observed a t - 1. 13 V; t he abnormal shape of t he anodic peak suggests
some i nt eract i on wi t h mercury. Similar results are obt ai ned in MeCN and THF;
t he redox potentials are - 1. 19 and - 1. 20 V, respectively. In cyclic vol t ammet ry
in DMF at a HMDE, I presents a cathodic peak with Epc = - 2. 7 V and an anodic
peak with Epa = -1. 1. V.
417
TABLE 1
Se l e n i u m der i vat i ves i s ol at ed whe n Se (2 10 -3 mol ) was pa r t i a l l y r e duc e d i n a pr ot i c medi a.
Two e qui va l e nt s of be nz yl chl or i de wer e a dde d be f or e or a f t e r el ect r ol ys i s
En t r y So l v e n t 103 Q/ F mo l - ' I s ol a t e d Cur r e nt
c o mp o u n d e f f i c i e nc y
( mol x 103) (%) a
1 DMF b,c 0. 97 I ( 0. 123) 25
I I ( 0. 143) 29
2 DMF c,d 2. 43 I ( 1. 05) 86 e
II ( 0. 12) 10
3 Me CNd , f 1. 02 I ( 0 . 5 1 ) 100
4 THF d, f 1. 73 I ( 0. 16) 18
a F r o m ' H NMR dat a.
b Be nz yl c hl or i de was a dde d a f t e r el ect r ol ys i s .
c Appl i e d p o t e n t i a l : - 1 . 1 V.
d Be nz yl c hl or i de was a dde d be f or e el ect r ol ys i s .
e 71% a f t e r TLC.
f Appl i e d p o t e n t i a l : - 1 . 2 V.
- 2
=L
~ o
I I I t
- 0 . 5 - 0 . 9 - 1 3 - 1 7
E/V
Fi g. 1. Re p e t i t i v e cycl i c v o l t a mmo g r a m o f di be nz yl di s el eni de ( 10 -3 M) i n DMF at a HMDE.
The scan r at e was 0. 1 V s - ' .
DI SCUSSI ON
Ent r y 1 of Tabl e 1 shows t hat in DMF t he f or mat i on of Se~- and Se ~- at
- 1 . 1 V pr oceeds c onc omi t a nt l y even i f t he el ect rol ysi s is s t oppe d bef or e t he
c ons umpt i on of one el ect ron. These ani ons l ead r espect i vel y t o II and I by t he
addi t i on of benzyl chl ori de. The moder at e yi el ds of I and II ma y arise f r om re-
oxi dat i on of t he ani oni c speci es by resi dual oxygen, or f r om mi grat i on of t hese
species t owar ds t he anodi c compar t ment . A deposi t of Se powde r was obser ved
418
in t he cent ral c ompa r t me nt of t he H- t ype cell, whi ch was not pr ot e c t e d against
air i nt r oduct i on. The set of resul t s obt ai ned when benzyl chl or i de was pr esent
duri ng el ect rol ysi s (ent ri es 2- - 4) and t he cycl i c vol t ammogr am of II (Fig. 1)
suggest t hat II is t he fi rst t o be el ect r ogener at ed. However , at t he pot ent i al ap-
pl i ed, it is f ur t her r educed t o I accordi ng t o r eact i ons (1) and (2).
2 e-
PhCH2SeSeCH~Ph . ~ 2 PhCH2Se- (1)
Hg electrode
II
2 PhCH2Se- + 2 PhCH2C1 -~ 2 PhCH2SeCH2Ph + 2 C1- (2)
I
The di sel eni de II was i sol at ed in a l ow yi el d in DMF ( ent r y 2). However , t he
fol l owi ng st r at egy whi ch we have t es t ed al l ows its el ect r ogener at i on in a high
yi el d, in a conveni ent one- pot el ect r osynt hesi s. The cat hode pot ent i al is initial-
l y f i xed at - 1 . 2 V, wher e I is el ect r ogener at ed, t hen moved t o - 2 . 3 V, wher e
t he excess of benzyl chl or i de is r educed t o t ol uene, and fi nal l y t o - 2 . 7 V wher e
r educt i ve cleavage of I leads t o PhCH2Se- and t ol uene. The oxi dat i on of t he se-
l eni de ani on ei t her by air or by st eppi ng t he pot ent i al t o - 1 V (see Fig. 1) l eads
t o II.
The above resul t s show t hat t he el ect r or educt i on of sel eni um at a mer cur y
pool cat hode is a pract i cal me t hod of access t o Se~- and Se 2- di ani ons. When
t he el ect rol ysi s is carri ed out in t he pr esence of an al kyl hal i de such as benzyl
hal i de, a di al kyl di sel eni de is i ni t i al l y el ect r ogener at ed. Dependi ng on t he val ues
of its r edox pot ent i al at a Hg el ect r ode compar ed t o t he wor ki ng pot ent i al , i t
mi ght be f ur t her r educed t o di al kyl sel eni de.
ACKNOWLEDGEMENT
We are grat eful t o Mrs. Fo u q u e t f or her t echni cal assistance.
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