Synthesis and reactions of mixed halide dialkyldithiophosphate derivatives of bismuth(III)

Abstract

Mixed chloride dialkyldithiophosphates of bismuth(III), [(RO)₂PS₂]_n BiCl_3-n (n = 1, 2; R = Et, Prⁿ, Prⁱ and Buⁱ) have been synthesized for the first time by the reactions of bismuth trichloride with sodium diisopropyldithiophosphate or alternatively by co-disproportionation reactions of bismuth trichloride with bismuth tris(dialkyldithiophosphates) in different stoichiometric ratios in suitable organic solvents. Monohalobismuth bis(diisopropyldithiophosphates) have also been synthesized by the cleavage reactions of bismuth tris(dialkyldithiophosphates) with bromine or iodine in 2:1 molar ratio. These new derivatives have been characterized by elemental analysis, molecular weight determinations (both cryoscopic and ebullioscopic) as well as spectroscopic (IR, ¹H NMR and ³¹P NMR) studies. On the basis of these data chelated structures with bidentate dialkyldithiophosphate groups have been proposed for these monomeric derivatives. Hydrolysis reactions of some of these compounds have also been studied.