| Abstract: | The reactions between either BiBr2Ph and Na/KMo(CO)3(η? C5H5)], BiPh{Mo(CO)3(η? C5H5)}2] and BiBr2Ph, or BiBr3 and BiPh3 and Bi{Mo(CO)3(η? C5H5)}3] afford the complex BiBrPh{Mo(CO)3(η? C5H5)}] 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(η? C5H5) 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 BiBr2Ph{Mo(CO)3(η? C5H5)}]? 3 ? although prolonged reaction results in the complex BiBr2{Mo(CO)3(η? C5H5)}2]? 5 ? which was characterised by X-ray crystallography as its Ph4P]+ salt. Complex 5 ? comprises a mononuclear bismuth centre bonded to two bromine atoms and two Mo(CO)3(η? C5H5) fragments in a geometry which lies between equatorially vacant trigonal bipyramidal and tetrahedral. The complex PPN]2Bi2Cl6{Mo(CO)3(η? C5H5)}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(η? C5H5) fragments in the apical positions on opposite sides of the Bi2Cl6 plane. |
