69656-94-6Relevant academic research and scientific papers
Reactivity of the bridged-sulfide complex Pd2Cl 2(μ-S)(μ-dmpm)2 toward electrophiles
Pamplin, Craig B.,Rettig, Steven J.,Patrick, Brian O.,James, Brian R.
, p. 1991 - 2002 (2012)
The dipalladium(i) complex Pd2Cl2(dmpm)2 (1a) [dmpm = bis(dimethylphosphino)methane] is known to react with elemental sulfur (S8) to give the bridged-sulfide complex Pd2Cl 2(μ-S)(dmpm)2 (2a) but, in the presence of excess S8, PdCl2[P,S-dmpm(S)] (4a) and dmpm(S)2 are generated. Treatment of 1a with elemental selenium (Se8), however, gives only Pd2Cl2(μ-Se)(dmpm)2 (3a). Complex 4a is best made by reaction of trans-PdCl2(PhCN)2 with dmpm(S). Complex 2a reacts with MeI to yield initially Pd2I 2(μ-S)(dmpm)2 and MeCl, and then Pd2I 2(μ-I)2(dmpm)2 and Me2S, whereas alkylation of 2a with MeOTf generates the cationic, bridged-methanethiolato complex [Pd2Cl2(μ-SMe)(dmpm)2]OTf (5). Oxidation of 2a with m-CPBA forms a mixture of Pd2Cl 2(μ-SO)(dmpm)2 and Pd2Cl2(μ- SO2)(dmpm)2, whereas Pd2Br2(μ-S) (dmpm)2 reacts selectively to give Pd2Br 2(μ-SO)(dmpm)2 (6b). Treatment of the Pd 2X2(μ-S)(dmpm)2 complexes with X2 (X = halogen) removes the bridged-sulfide as S8, with co-production of PdII(dmpm)-halide species. X-ray structures of 3a, 5 and 6b are presented. Reactions of dmpm with S8 and Se8 are clarified. Differences in the chemistry of the dmpm systems with that of the corresponding dppm systems [dppm = bis(diphenylphosphino)methane] are discussed.
