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

Addition of phenyldi(2-thienyl) phosphine (PPhTh2) to [Re-2(CO)(10-n)(NCMe)(n)] (n = 1, 2) affords the substitution products [Re-2(CO)(10-n)(PhPTh2)(n)] (1, 2) together with small amounts of fac-[ClRe(CO)(3)(PPhTh2)(2)] (3) (n = 2). Reaction of [Re-2(CO)(10)] with PPhTh2 in refluxing xylene affords a mixture which includes 2, [Re-2(CO)(7)(PPhTh2)(mu-PPhTh)(mu-H)] (4), [Re-2(CO)(7)(PPhTh2)(mu-PPhTh)(mu-eta(1), kappa(1)(S)-C4H3S)] (5) and mer[HRe(CO)(3)(PPhTh2)(2)] (6). Phosphido-bridged 4 and 5 are formed by the carbon-phosphorus bond cleavage of the coordinated PPhTh2 ligand, the cleaved thienyl group being retained in the latter. Reaction of [Mn-2(CO)(10)] with PPhTh2 in refluxing toluene affords [Mn-2(CO)(9)(PPhTh2)] (7) and the carbon-phosphorus bond cleavage products [Mn-2(CO)(6)(mu-PPhTh)(mu-eta(1),eta(5)-C4H3S)] (8) and [Mn-2(CO)(5)(PPhTh2)(mu-PPhTh)(mu-eta(1),eta(5)-C4H3S)] (9). Both 8 and 9 contain a bridging thienyl ligand which is bonded to one manganese atom in a eta(5)-fashion. (C) 2009 Elsevier B. V. All rights reserved.