Phenylation of Organic Derivatives of Mercury, Silicon, Tin, and Bismuth with Pentaphenylantimony and Pentaphenylphosphorus

Article abstract of DOI:10.1023/A:1024731719528

Pentaphenylantimony and -phosphorus react with arylmercury chlorides in toluene at room temperature to give diaryl derivatives of mercury in yields of up to 95%. The reactions of pentaphenylantimony and -phosphorus with silicon and tin halides involve ary

Full text of DOI:10.1023/A:1024731719528

Russian Journal of General Chemistry, Vol. 73, No. 2, 2003, pp. 202 203. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 2, 2003,
pp. 222 223.
Original Russian Text Copyright
2003 by Sharutin, Sharutina, Senchurin, Egorova, Ivanenko, Petrov.
Phenylation of Organic Derivatives of Mercury, Silicon, Tin,
and Bismuth with Pentaphenylantimony
and Pentaphenylphosphorus
V. V. Sharutin, O. K. Sharutina, V. S. Senchurin,
I. V. Egorova, T. K. Ivanenko, and B. I. Petrov
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received February 8, 2001
Abstract Pentaphenylantimony and -phosphorus react with arylmercury chlorides in toluene at room
temperature to give diaryl derivatives of mercury in yields of up to 95%. The reactions of pentaphenylanti-
mony and -phosphorus with silicon and tin halides involve arylation of the latter in yields of up to 79%. The
products of the reaction of pentaphenylphosphorus with triphenylbismuth dihalides are tetraphenylphosphorus
halides, triphenylbismuth, and halobenzene.
It is known that pentaarylantimony and pentaphe-
nylbismuth effectively arylate organic derivatives of
tin, antimony, and bismuth [1 7]. Continuing research
into the arylating action of pentaphenyl derivatives of
antimony and phosphorus, we have studied their re-
actions with mercury, silicon, tin, and bismuth aryl
halides.
effectively arylates organotin halides [6]. We found
that the reactions of pentaphenylphosphorus with tri-
butyltin chloride and of pentaphenylantimony with
tris(pentafluorophenyl)silicon
similarly.
bromide
proceed
Ph5P + Bu3SnCl
Ph4PCl + Bu3SnPh,
It was shown that treatment of phenylmercury
chloride with pentaphenylantimony and -phosphorus
leads to phenylation of the former. Diphenylmercury
and tetraphenylantimony(-phosphorus) chloride were
isolated from the reaction mixtures in yields of up
to 78%.
Ph5Sb + (C6F5)3SiBr
Ph4SbBr + (C6F5)3SiPh.
The above reactions proceed in toluene either for
1 h at 100 C or for 24 h at room temperature. The
yields of organotin and organosilicon products are 73
and 61%, respectively.
Ph5E + PhHgCl
Ph2Hg + Ph4ECl,
The reactions of triphenylbismuth dihalides with
pentaphenylphosphorus under analogous conditions
gave tetraphenylphosphorus halide, triphenylbismuth,
and halobenzene. The latter products are evidently
formed by decomposition of the labile tetraphenyl-
bismuth halide.
E = Sb, P.
These reactions proceed in toluene at 100 C for 1 h.
Coarse crystals of tetraphenylantimony(-phosphorus)
chloride are formed.
The reaction of pentaphenylantimony with ferro-
cenylmercury chloride under the same conditions
resulted in quantitative formation of tetraphenylanti-
mony chloride, diferrocenylmercury, and diphenyl-
mercury. The symmetrical mercury derivatives are
probably formed via intermediate formation of ferro-
cenyl(phenyl)mercury.
Ph5P + Ph3BiX2
Ph4PX + Ph3Bi + PhX,
X = Cl, Br.
The resulting aryl derivatives were simiar in proper-
ties (melting points, IR spectra, TLC) to the same
compounds obtained by other methods.
FcHgCl + Ph5Sb
Ph4SbCl + FcHgPh
EXPERIMENTAL
All the reactions were carried out in evacuated
glass ampules according to the following typical pro-
cedures.
1/2Fc2Hg + 1/2Ph2Hg
It was previously shown that pentaarylantimony
1070-3632/03/7302-0202$25.00 2002 MAIK Nauka/Interperiodica

PHENYLATION OF ORGANIC DERIVATIVES OF MERCURY, SILICON, TIN, AND BISMUTH
203
Diphenylmercury. a. A mixture of 2.00 g of penta- matographed on Silica gel L 5/40, eluent petroleum
phenylantimony, 1.23 g of phenylmercury chloride,
and 10 ml of toluene was heated at 100 C for 1 h. The
crystals that formed were filtered off, washed with
petroleum ether, and dried to obtain 1.60 g (87%) of
tetraphenylantimony chloride, mp 198 C. The solvent
was removed from the filtrate, and the residue was
chromatographed on Silica gel L 5/40, eluent petro-
leum ether. Diphenylmercury, 1.10 g (78%), was ob-
tained, mp 122 C (mp 125 C [9]).
ether. Tributylphenyltin, 0.64 g (73%) was obtained.
Reaction of pentaphenylphosphorus with triphe-
nylbismuth dichloride. A mixture of 0.50 g of pen-
taphenylphosphorus, 0.61 g of triphenylbismuth di-
chloride, and 30 ml of toluene was heated at 100 C
for 1 h. The reaction mixture was cooled, the solvent
was removed, and the residue was treated with petro-
leum ether (3 50 ml). The substance insoluble in
petroleum ether was tetraphenylphosphorus chloride,
0.40 g (89%), mp 262 C. The ethereal extracts were
evaporated to isolate 0.52 g (98%) of triphenylbis-
muth, mp 72 C.
b. A mixture of 1.00 g of pentaphenylphosphorus,
0.75 g of phenylmercury chloride, and 6 ml of tolu-
ene was kept at room temperature for 24 h. The crys-
tals that formed were filtered off, washed with petro-
leum ether, and dried to obtain 0.82 g (90%) of tetra-
phenylphosphorus chloride. The solvent was removed
from the filtrate, and the residue was chromatographed
on Silica gel L 5/40, eluent petroleum ether. Diphenyl-
mercury, 0.80 g (94%), was obtained, mp 122 C
(mp 125 C [9]).
Reaction of pentaphenylphosphorus with triphe-
nylbismuth difluoride was performed in a similar
way. Tetraphenylphosphorus bromide (84%) and tri-
phenylbismuth (96%) were isolated.
Reaction of pentaphenylphosphorus with triphe-
nylbismuth difluoride was performed in a similar
way. Tetraphenylphosphorus fluoride (98%) and tri-
phenylbismuth (96%) were isolated.
Reaction of pentaphenylantimony with ferro-
cenylmercury chloride. A mixture of 0.28 g of ferro-
cenylmercury chloride, 0.34 g of pentaphenylanti-
mony, and 5 ml of toluene were heated at 90 C for
1 h. The crystals that formed were filtered off, washed
with petroleum ether, and dried to obtain 0.30 g
(96%) of tetraphenylantimony chloride. The solvent
was removed from the filtrate, and the residue was
chromatographed on Silica gel L 5/40, eluent petro-
leum ether. Diphenylmercury, 0.11 g (92%), was ob-
tained, mp 122 C (mp 125 C [9]). The product in-
soluble in petroleum ether was recrystallized from
toluene to obtain 0.18 g (95%) of diferrocenylmercury,
mp 237 C.
REFERENCES
1. Sharutin, V.V., Senchurin, V.S., Sharutina, O.K., Pa-
kusina, A.P., and Panova, L.P., Zh. Obshch. Khim.,
1996, vol. 66, no. 10, pp. 1755 1756.
2. Sharutin, V.V., Sharutina, O.K., Panova, L.P., and
Bel’skii, V.K., Zh. Obshch. Khim., 1997, vol. 67, no. 9,
pp. 1531 1535.
3. Sharutin, V.V., Sharutina, O.K., Pakusina, A.P., and
Bel’skii, V.K., Zh. Obshch. Khim., 1997, vol. 67, no. 9,
pp. 1536 1541.
4. Sharutin, V.V., Sharutina, O.K., Egorova, I.V., and
Panova, L.P., Zh. Obshch. Khim., 1998, vol. 68, no. 2,
pp. 345 346.
5. Sharutin, V.V., Sharutina, O.K., Egorova, I.V., Sen-
churin, V.S., Zakharova, A.N., and Bel’skii, V.K., Zh.
Obshch. Khim., 1999, vol. 69, no. 9, pp. 1470 1473.
6. Sharutin, V.V., Sharutina, O.K., Senchurin, V.S., Ko-
valeva, T.A., Shcherbakov, V.I., and Gladysheva, E.N.,
Zh. Obshch. Khim., 2000, vol. 70, no. 1, pp. 69 70.
Phenyltris(pentafluorophenyl)silane. A mixture
of 0.60 g of tris(pentafluorophenyl)silicon bromide,
0.50 g of pentaphenylantimony, and 5 ml of toluene
was heated at 100 C for 1 h. Then the reaction mix-
ture was cooled to room temperature, and the crystals
that formed were filtered off, washed with petroleum
ether, and dried to obtain 0.37 g (74%) of tetraphenyl-
antimony bromide. The solvent was removed from
the filtrate, and the residue was chromatographed on
alumina, eluent petroleum ether. 0.37 g (61%) of
crystals were obtained, mp 48 C.
7. Sharutin, V.V., Sharutina, O.K., Egorova, I.V., Khar-
sika, A.N., Lodochnikova, O.A., Gubaidullin, A.T., and
Litvinov, I.A., Izv. Ross. Akad. Nauk, Ser. Khim., 1999,
no. 12, pp. 2350 2354.
8. Sharutin, V.V., Sharutina, O.K., Tarasova, T.A., Khar-
sika, A.N., and Bel’skii, V.K., Zh. Obshch. Khim., 1999,
vol. 69, no. 12, pp. 1979 1981.
Tributylphenyltin. A mixture of 1.00 g of penta-
phenylphosphorus, 0.78 g of tributyltin chloride, and
6 ml of toluene was kept at room temperature for 24 h.
The crystals that formed were filtered, washed with
petroleum ether, and dried to obtain 0.71 g (79%) of
tetraphenylphosphorus chloride. The solvent was re-
moved from the filtrate, and the residue was chro-
9. Makarova, L.G. and Nesmeyanov, A.N., Metody ele-
mentoorganicheskoi khimii. Rtut’ (Methods of Organo-
element Chemistry. Mercury), Moscow: Nauka, 1965,
p. 245.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 2 2003