Synthetic and structural Studies on Organomolybdenum‐Bismuth Halide Complexes

The reactions between either BiBr 2 Ph and Na/K[Mo(CO) 3 (ηC 5 H 5 )], [BiPh{Mo(CO) 3 (ηC 5 H 5 )} 2 ] and BiBr 2 Ph, or BiBr 3 and BiPh 3 and [Bi{Mo(CO) 3 (ηC 5 H 5 )} 3 ] afford the complex [BiBrPh{Mo(CO) 3 (ηC 5 H 5 )}] 1 which has been characterised by X‐ray crystallography. Complex 1 comprises a bismuth centre bonded to a bromine atom, a phenyl group and a Mo(CO) 3 (ηC 5 H 5 ) fragment together with a longer secondary intermolecular interaction between a bromine from an adjacent molecule which results in a one‐dimensional polymeric structure. Addition of a source of bromide anion to 1 affords the anionic complex [BiBr 2 Ph{Mo(CO) 3 (ηC 5 H 5 )}] − 3 − although prolonged reaction results in the complex [BiBr 2 {Mo(CO) 3 (ηC 5 H 5 )} 2 ] − 5 − which was characterised by X‐ray crystallography as its [Ph 4 P] + salt. Complex 5 − comprises a mononuclear bismuth centre bonded to two bromine atoms and two Mo(CO) 3 (ηC 5 H 5 ) fragments in a geometry which lies between equatorially vacant trigonal bipyramidal and tetrahedral. The complex [PPN] 2 [Bi 2 Cl 6 {Mo(CO) 3 (ηC 5 H 5 )} 2 ] 8 has also been synthesised and characterised by X‐ray crystallography. A dimeric dianion is observed which can be viewed as two edge‐shared square‐based pyramids with chlorine atoms in the basal planes and Mo(CO) 3 (ηC 5 H 5 ) fragments in the apical positions on opposite sides of the Bi 2 Cl 6 plane.