Syntheses and Characterization of Bromo- and Chloro(phthalocyaninato)bismuth(III) Complexes

Abstract By the reactions of BiX3 (X = Cl−, Br−, I−, and NO3−) with Li2(pc) (pc = phthalocyaninate dianion, C32H16N82−) in dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, and acetone, [Bi(pc)X] complexes have been produced. These complexes were also produced by heating a mixture of BiX3 and phthalonitrile. Among them, [Bi(pc)Cl] and [Bi(pc)Br] were isolated for the first time as a phthalocyanine complex of group-15 elements and successfully characterized by elemental analyses, solution chemistry, electronic and IR spectroscopy. The latter two complexes were soluble in polar solvents, but were insoluble in nonpolar solvents. In solutions, bismuth(III) in [Bi(pc)X] was labile and was readily expelled from a pc ring by a trace amount of water, acids, and bases, and it was replaced by a divalent transition metal upon the addition of MSO4 (M = cobalt(II), nickel(II), copper(II), and zinc(II)) forming [M(pc)]. The electronic and IR spectra of the [Bi(pc)X]s were characteristic of the usual metallophthalocyanines, except that a hyper metal-to-ligand charge-transfer band appeared in their electronic spectra.