Transition-metal-substituted dichlorobismuthanes as starting materials for novel bismuth -: Transition-metal clusters

The reaction of [{Cp(CO)(2)Fe}BiCl2] (la) with [Co(CO)(4)](-) leads to the formation of the first heteroleptic substituted bismuthane, [(mu(3)-Bi){Co(CO)(4)}(2){Fe(CO)(2)Cp}] (2). When the open complex 2 is irradiated, the heterocubane [Bi-4{Co(CO)(3)}(4)] (3) is formed. [{Cp (CO)(2)Fe}BiCl2] (Ib; Cp = eta(5)-C5H3-tBu(2)) reacts with [Fe(CO)(4)](2-) to give the nido cluster [{Fe-3(CO)(9)}{mu-BiFe(CO)(2)Cp }(2)] (4) and to give the complex [Bi-4{mu(3)-Fe(CO)(3)}(3){Fe(CO)(2)Cp }(2)] (5); the latter contains a distorted-tetrahedral Bi-4 cluster core in which three of the faces are capped by Fe(CO)(3) moieties. The reaction of Ib with Na-2[W-2(CO)(10)] yields the Bi-bridged tetrahedral W2Bi2 cluster [{W-2(CO)(8)}(mu,eta(2)-Bi-2){mu-BiFe(CO)(2)Cp }] (6). In contrast to this, the molybdenum-substituted analogue [{Cp (CP)(3)Mo}BiCl2] (7) reacts with Na-2[Fe(CO)(4)] to yield the arachno cluster [{Fe-2(CO)(6)}{Fe(CO)(4)}{mu(3)-BiMo(CP)(3)Cp }(2)] (9). When 7 is reacted with Na-2[W(CO)5], the complex [{Cp (CO)(3)Mo}(2)BiCl] (10) is obtained. The decomposition of compound 7 in THF leads to the ionic complex [(Cp MoCO)(2)(mu-Cl)(3)](2)[Bi2Cl8(thf)(2)] (8). The crystal structures of all products are presented.