Diphenyl(trifluoromethyl)bismuth and phenylbis(trifluoromethyl)bismuth—new organoperfluoroalkyl derivatives of tervalent bismuth

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Journal of Organometaliic Chemrstry, 417 (1991) C47-C49 Elsevier Sequoia S.A.. Lausanne

JOM 22191PC Preliminary

communication

Diphenyl( trifluoromethyl) bismuth and phenylbis( trifluoromethyl)bismuth-new organoperfluoroalkyl derivatives of tervalent bismuth Sergej Pasenok Institute of Organic Chemistty,

Academy

of Sciences o.f the Ukramian

SSR,

Murmanskuya

5, Kiev-94

(USSR)

Dieter

Naumann

* and Wieland

Instltut ftir Anorganische (Received

Chemie,

Tyrra

Uniuersitiit LU Kiiln, Greinstr. 6, W-5000 Kiiln 41 (Germany)

April 22nd, 1991)

Abstract

Diphenyl(trifluoromethyl)bismuth and phenylbis(trifluoromethyl)bismuth have been synthesized from Cd(CF,),.2CH,CN and the corresponding phenylbismuth halides. The reactions of the new compounds are similar to those of tris(perfluoroorgano)bismuth compounds and mixed phenyl-alkyl bismuth derivatives.

Tris(perfluoroorgano)bismuth derivatives are available reactions of BiCl 3 or BiBr, with bis(perfluoroorgano)cadmium 2 BiX? + 3 Cd(R,),

.2D + 2 Bi(R,),

in good yields from complexes [l].

the

+ 3 CdX,

(X: Cl, Br; R,: C,IF2n+l (n = 1, 2, 3, 4, 6, 8), C,F,;

D: unidentate

ligand).

These derivatives, especially tris(trifluoromethyl)bismuth, are excellent perfluoroalkyl-group transfer reagents, comparable in properties to those of the cadmium compounds and, in addition, more selective. This was shown by the reactions with AgNO, to give Ag[Ag(CF,),], with C,H5COCl to give C,H,COCF,, and with halogens or interhalogen compounds to give the corresponding trifluorohalogenomethane [2]. In order to develop new polar trifluoromethyl group transfer reagents we decided to make the previously unknown C,H,Bi(CF3), and (C,H,),BiCFx. The compounds were prepared as shown in the following equations: C,H,BiBr,

+ Cd(CF,),

2 (C,H,),BiCl

.2CH,CN

+ Cd(CF,),

.2CH,CN

rTry;‘d”d) C,H,Bi(CF3)*

+ CdBr, .2CH,CN

2% 2 (C,H,),BiCF,

0022-328X/91/$03.50

0 1991 - Elsevier Sequoia

S.A. All rights reserved

+ CdCl, .2CH,CN

Experimental

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19F NMR spectra (Bruker Spectral data of (C,H,),BiCF, and C,H,Bi(CF,),. AC 200, 19F: 188.3 MHz, CC1,F ext., CH,CN) (C,H,),BiCF,: 6 -38.6 ppm, ‘J(‘9F-‘3C) = 390.8 Hz, ‘A(19F- ‘2”3C) 0.127 ppm, C,H,Bi(CF,),: 6 - 36.2 ppm, ‘J(‘9F-‘3C) = 389.1 Hz, ‘A(19F- ‘2”13C) 0 .127 ppm, splitting of the 13C satellites into quartets, 4J(‘9F-‘9F) = 4.8 Hz. (Bi(CF,),: 6 - 33.9 ppm, ‘J(‘9F-‘3C) = 390.5 Hz, ‘A(‘9F-‘2/‘3C) 0.139 ppm, splitting of the 13C satellites into septets, 4f(‘9F-‘9F) = 4.7 Hz [l]). Mass spectrum (Varian CH5 (modified), EI, 13 eV, 75°C). (C,H,),BiCF3: 432 9.7%), 413 ((C,H,),BiCFzf, l.O’%), 363 ((C6H5)2Bii, lOO%), 355 ((C,H,),BiCF:, 21.2%), 336 ((C,H,)BiCF:, 13.7%), 286 ((C,H,)Bi+, 78.4%), 209 ((C,H,)BiCF;, (si’;. X4%,\. I54 zBK1 anb &X,-B>BT, a& 0~ EGb%cz-Xertz-S_?j&mg fn~ a ~XZZQ 10 S.2 The financial support of the Minister fiir Wissenschaft und Forschung des Landes Nordrhein--Westfalen and the Fonds der Chemischen Industrie is gratefully acknowledged. References 1 2 3 4

D. W. T. M.

Naumann and W. Tyrra, J. Organomet. Chem., 334 (1987) 323. Tyrra and D. Naumann, Can. J. Chem., 67 (1989) 1949. Kauffmann and F. Steinseifer, Chem. Ber., 118 (1985) 1931. Wieber and I. Sauer, Z. Naturforsch., 40b (1985) 1476.