Transition-Metal-Substituted Dichlorobismuthanes as Starting Materials for Novel Bismuth−Transition-Metal Clusters

Abstract

The reaction of [BiCl2] (1a) with [Co(CO)4]- leads to the formation of the first heteroleptic substituted bismuthane, [(μ3-Bi)2] (2). When the “open” complex 2 is irradiated, the heterocubane [Bi44] (3) is formed. [BiCl2] (1b; Cp‘ ‘ = η5-C5H3-tBu2) reacts with [Fe(CO)4]2- to give the nido cluster [2] (4) and to give the complex [Bi432] (5); the latter contains a distorted-tetrahedral Bi4 cluster core in which three of the faces are capped by Fe(CO)3 moieties. The reaction of 1b with Na2[W2(CO)10] yields the Bi-bridged tetrahedral W2Bi2 cluster [(μ,η2-Bi2)] (6). In contrast to this, the molybdenum-substituted analogue [BiCl2] (7) reacts with Na2[Fe(CO)4] to yield the arachno cluster [2] (9). When 7 is reacted with Na2[W(CO)5], the complex [2BiCl] (10) is obtained. The decomposition of compound 7 in THF leads to the ionic complex [(Cp‘ ‘MoCO)2(μ-Cl)3]2[Bi2Cl8(thf)2] (8). The crystal structures of all products are presented.