Coordinatively unsaturated complexes [M 2(CO) 4(μ-H)(μ-P tBu 2)(μ-Ph 2PCH 2PPh 2)] (MFe, Ru): synthesis and crystal structures of [Fe 2(CO) 4(μ-H)(μ-SO)(μ-P tBu 2)(μ-Ph 2PCH 2PPh 2)] and [Ru 2(CO) 4(μ-H)(μ-SO 2)(μ-P tBu 2)(μ-Ph 2PCH 2PPh 2)

Abstract

[Fe 2(CO) 4(μ-H)(μ-P tBu 2)(μ-dppm)] ( 1a) reacts with elemental sulfur to give [Fe 2(CO) 4(μ-H)(μ-S)(μ-P tBu 2)(μ-dppm)] ( 2a) (dppm=Ph 2PCH 2PPh 2). The reaction of 1a with CCl 4 or CHCl 3 affords spontaneously in nearly quantitative yield [Fe 2(CO) 4(μ-Cl)(μ-P tBu 2)(μ-dppm)] ( 3a). [Ru 2(CO) 4(μ-H)(μ-P tBu 2)(μ-dppm)] ( 1b) reacts with SO 2 in THF under normal conditions to [Ru 2(CO) 4(μ-H)(μ-SO 2)(μ-P tBu 2)(μ-dppm)] ( 5b). 5b is also formed by oxidation of the sulfido ligand in [Ru 2(CO) 4(μ-H)(μ-S)(μ-P tBu 2)(μ-dppm)] ( 2b) by means of 3-chloroperoxybenzoic acid or H 2O 2 as oxidizing reagent. As the primary oxidation products of 2a or 2b the sulfur monoxide complexes [M 2(CO) 4(μ-H)(μ-SO)(μ-P tBu 2)(μ-dppm)] (MFe, 4a; MRu, 4b) are obtained by using 3-phenyl-2-(phenylsulfonyl)-oxaziridine as oxidizing reagent. The molecular structures of 4a and 5b were confirmed by crystal structure analyses.