Insertion of indium(I) into carbon-halogen bonds

INORG.

NUCL.

CHEM.

LETTERS

Vol. 7, pp. 403-404,

1971.

Pergamon

Press.

Printed

in

Great

INSERTION OF INDIUM(I) INTO CARBON-HALOGEN BONDS L.WATERWORTH AND I.J.WORRALL Department of Chemistry, The University, Lancaster ( R e c e i v e d ~ November 1970)

Abstract

Indium(I) undergoes oxidative addition reactions with methyl bromide and iodide to form indium-carbon bonds. We have recently demonstrated that gallium(I) readily inserts into carbon-halogen bonds (I'2).

The chemical

similarity between In2Br 4 and Ga2Br4, e.g. they both form complexes of type ML~Br; (3) and are strong reducing agents, suggests that indium(I) compounds may undergo such oxidative addition reactions. Methyl bromide was added to In2Bm 4 in vacuo and allowed to stand for one hour.

Excess methyl bromide was removed

and the mass spectrum and Raman spectrum of the product examined. The mass spectrum included major peaks corresponding to the following species:

In2Brs, In2Br4Me, In2Br3Me2,

In2Br3Me and In2Br2Me. This suggests that the oxidative addition reaction In2Br 4 + MeBr ÷ In2BrsMe has occurred.

The presence of a Raman band at 523 cm -I

confirms the presence of a carbon-indium bond.

(For MeInCl 2

(In-C) 523 cm-l) (4). The product may either be a single compound MeIn?Br 5 403

Britain.

INSERTION OF INDIUM(l) INTO CARBON-HALOGEN BONDS

404

Vol. 7, No. 5

or a mixture of In2Br 6 and Me2In2Brq. A similar reaction occurs with methyl iodide although here complications occur due to halogen exchange.

Significant

peaks in the mass spectrum correspond to In2Bm3IMe , In2BrIMe , InI2Me and InI 3.

The presence of an In-C bond is again

indicated by a Raman band aT 518 cm -I. In2Br q was prepared by the method described in reference

References (i) W.Lind and I.J.Worrall,

Chem.Comm.,

1969, 829.

(2) W.Lind and I.J.Worrall, to be published. (3) P.L.Goggin and I.J.McColm, J.Inorg.Nuclear 28, 250. (q) H.C.Clark and A.L.Pickard, 68.

Chem., 1966,

J.Organometal.Chem.,

1968, 13,

3.