Reactivity of phenyldi(2-thienyl)phosphine towards group 7 metal carbonyls: Carbon–phosphorus bond activation

Abstract

Addition of phenyldi(2-thienyl)phosphine (PPhTh 2) to [Re 2(CO) 10− n (NCMe) n ] ( n = 1, 2) affords the substitution products [Re 2(CO) 10− n (PhPTh 2) n ] ( 1, 2) together with small amounts of fac-[ClRe(CO) 3(PPhTh 2) 2] ( 3) ( n = 2). Reaction of [Re 2(CO) 10] with PPhTh 2 in refluxing xylene affords a mixture which includes 2, [Re 2(CO) 7(PPhTh 2)(μ-PPhTh)(μ-H)] ( 4), [Re 2(CO) 7(PPhTh 2)( μ-PPhTh)(μ-η 1,κ 1(S)-C 4H 3S)] ( 5) and mer-[HRe(CO) 3(PPhTh 2) 2] ( 6). Phosphido-bridged 4 and 5 are formed by the carbon–phosphorus bond cleavage of the coordinated PPhTh 2 ligand, the cleaved thienyl group being retained in the latter. Reaction of [Mn 2(CO) 10] with PPhTh 2 in refluxing toluene affords [Mn 2(CO) 9(PPhTh 2)] ( 7) and the carbon–phosphorus bond cleavage products [Mn 2(CO) 6(μ-PPhTh)(μ-η 1,η 5-C 4H 3S)] ( 8) and [Mn 2(CO) 5(PPhTh 2)(μ-PPhTh)(μ-η 1,η 5-C 4H 3S)] ( 9). Both 8 and 9 contain a bridging thienyl ligand which is bonded to one manganese atom in a η 5-fashion.