Neutral and anionic aryloxy halides of bismuth(III)

The preparation and crystal structures of the aryloxy bismuth halide compou nds [Bi2Cl4(thf)(2)(mu-OC6H3Me2-2,6)(2)], [Bi2Cl4(thf)(2)(mu-OC6H2Me3-2,4,6 )(2)], [NMe4](2)[Bi-2(OC6H3Me2-2,6)(6)(mu-Cl)(2)] and [PPh4](2)[BiBr3(OC6H2 Me3-2,4, 6)(2)] are described. The former two compounds, which are isostruc tural, are neutral and comprise loosely bound polymers of more strongly bou nd dimers. Within the dimeric unit, the two bismuth centres are bridged by two aryloxide groups with each bismuth additionally carrying two chlorine a toms and one thf ligand. Asymmetric chlorine bridges between dimers result in the polymeric structure. The latter two structures contain aryloxy bismu th halide anions. In the structure of [Bi-2(OC6H3Me2-2,6)(6)(mu-Cl)(2)](2-) two chlorine atoms form bridges between Bi(OC6H3Me2-2,6)(3) units whereas in [BiBr3(OC6H2Me3-2,4,6)(2)](2-) a monomeric species is present. Also repo rted are the preparations of the compounds [PPh4](2)[Bi2Br2(OC6H2Me3-2,4,6) (4)(mu-Br)(2)], [PPh4](2)[BiBr2(OC6H3Me2-2,6)(3)] and SbCl2(OC6H2Bu3t-2,4,6 ).