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Reaction of RLi [R = CH(SiMe3)2] with BiCl3 in a 2:1 ratio gives R2BiCl (1). RBiPh2 is formed by the action of RMgCl on Ph2BiCl. Reaction of RBiPh2 with HCl in CHCl3 gives RBiCl2 (2), which crystallizes from diethyl ether as the solvate 2·0.5Et2O. The crystal structures of 1 and 2·0.5Et2O have been determined by X-ray diffraction. Crystals of 1 consist of pyramidal R2BiCl molecules, whereas in crystals of 2·0.5Et2O there are {[RBi(Cl)Cl]2·Et2O}x chains with chloro bridges. The diethyl ether molecules are weakly associated to neighboring bismuth atoms in the chain.

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CH 3 SbPh 2 reacts with HCl to give CH 3 SbCl 2 . CH 3 BiCl 2 and CH 3 BiBr 2 are formed by reaction of CH 3 -BiPh 2 with HCl or HBr. The adducts [CH 3 ECl 2 (bipy)] (E ) Sb, Bi, bipy ) 2,2′-bipyridine) are obtained by combining the components in diethyl ether or tetrahydrofuran. The crystal structures of CH 3 BiCl 2 and [CH 3 -ECl 2 (bipy)] (E ) Sb, Bi) have been determined by singlecrystal X-ray diffraction.