Alkylation of (As, Sb, Bi)Cl3: formation of [(As, Sb, Bi)RCl2], (E)-[BiR(CH2CHC)(SiMe3)(C5H4N-2)] and 2-CH(SiMe3)2C5H4N-5-R [R = C(SiMe3)2C5H4N-2]

Abstract

Monomeric alkyldichloro-antimony(III) and –bismuth(III) compounds [MRCl₂], R = C(SiMe₃)₂C₅H₄N-2′, and the thermally unstable arsenic(III) analogue are accessible from the appropriate group 15 trichloride and LiR in diethyl ether; treating BiCl₃ with two and three equivalents of LiR in tetrahydrofuran (THF) yields (E)-[BiR(CH₂CHC)(SiMe₃)(C₅H₄N-2)] where the C₂ insertion–SiMe₃ elimination fragment originates from THF, and the ‘head-to-tail’ alkyl coupled species, 2-CH(SiMe₃)₂C₅H₄N-5-R.