Dimeric polybismuth heteroanion of [Rh@Bi10(RhCO)5]2- built of Bi10-bowl and Rh@(Rh-CO)5 square pyramidal

Redox reaction of the monovalent Rh2(CO)4Cl2 and Binn- (n = 2, 3) from K5Bi4 in ethylenediamine (en) solution produced the decabismuthide-hexarhodium dianion [Rh@Bi10(RhCO)5]2- (1a) wherein a novel Bi10-bowl was constructed from oxidized 2Bi3/2Bi2 open triangles/dimers, which was stabilized by strong bonding to a reduced Rh@(RhCO)5 square pyramid. Two 1a dianons are held together by weak interactions (van der Waals forces and spatial resistance) to form a dimer [Rh@Bi10(RhCO)5]24- (1). The structure and bonding of the novel polybismuthide heteroanion 1 are discussed.