@article {11116,
	title = {{Reactions of the Bis(dialkylphosphino)methane Complexes Pd2X2(μ-R2PCH2PR2)2(X = halogen},
	journal = {Inorganic Chemistry},
	year = {2011},
	month = {07/2011},
	pages = {110722164832076},
	abstract = {The Pd2X2(dmpm)2 complexes [X = Cl (1a), Br (1b), I (1c); dmpm = bis(dimethylphosphino)methane. In all the dipalladium complexes mentioned in this paper, the dmpm, depm, and dppm ligands (unless stated otherwise) are bridging, but for convenience the μ-symbol is omitted.] react with H2S to yield H2 and the bridged-sulfido complexes Pd2X2(μ-S)(dmpm)2 (2a{\textendash}c), of which 2a and 2b are structurally characterized. With 1a, two rapid reversible equilibria are observed by NMR spectroscopy below -30 {\textdegree}C, and two reaction intermediates are detected; both are likely hydrido(mercapto) species. Reaction of 1a with 1 equiv of elemental sulfur also yields 2a. The reaction of 1a with COS results in the initial formation of Pd2Cl2(μ-COS)(dmpm)2 (3) that undergoes decarbonylation to yield 2a and Pd2Cl2(μ-CO)(dmpm)2 (4), which is also formed via reversible insertion of the CO into the Pd{\textendash}Pd bond of 1a. The solid-state molecular structure of the previously reported complex Pd2Cl2(μ-CS2)(dmpm)2 (5), together with solution NMR data for 3 and 5, reveal that the bridging heterocumulene ligands coordinate in an η2-C,S fashion. Analogous findings were made for the corresponding Pd2X2(depm)2 complexes [X = Cl (1a{\textquoteright}), Br (1b{\textquoteright}), I (1c{\textquoteright}); depm = bis(diethylphosphino)methane], although no μ-COS species was detected. The Pd2X2(μ-S)(depm)2 complex was structurally characterized. Differences in the chemistry of the previously studied, corresponding dppm systems (dppm = bis(diphenylphosphino)methane) are discussed.},
	issn = {1520-510X},
	doi = {10.1021/ic200503d},
	author = {Pamplin,Craig B. and Rettig, Steven J. and Patrick,Brian O. and James, Brian R.}
}
