Carbon−Phosphorus Bond Activation of Tri(2-thienyl)phosphine at Dirhenium and Dimanganese Centers

摘要: Reaction of [Re-2(CO)(9)(NCMe)] with tri(2-thienyl)phosphine (PTh3) in refluxing cyclohexane affords three substituted dirhenium complexes: [Re-2(CO)(9)(PTh3)] (1), [Re-2(CO)(8)(NCMe)(PTh3)] (2), and [Re-2(CO)(8)(PTh3)(2)] (3). Complex 2 was also obtained from the room-temperature reaction [Re-2(CO)(8)(NCMe)(2)] PTh3 is an unusual example which acetonitrile phosphine ligands are coordinated to same rhenium atom. Thermolysis 1 3 xylene [Re-2(CO)(8)(mu-PTh2)(mu-eta(1):kappa(1)-C4H3S)] (4) [Re-2(CO)(7)(PTh3)(mu-PTh2)(mu-H)] (5), respectively, both resulting carbon-phosphorus bond cleavage a ligand. [Re-2(CO)10] gives complex mixture products. These products include 3-5, two further binuclear products, [Re-2(CO)(7)(PTh3)(mu-PTh2)(mu-eta(1):kappa(1)-C4H3S)] (6) [Re-2(CO)(7)(mu-kappa(1):kappa(2)-Th2PC4H2SPTh)(mu-eta(1):kappa(1)-C4H3S )] (7), mononuclear hydrides [ReH(CO)(4)(PTh3)] (8) trans-[ReH(CO)(3)(PTh3)(2)] (9). Binuclear 6 structurally similar 4 can be latter equiv PTh3. Formation 7 involves series rearrangements formation unique new diphosphine ligand, Th2PC4H2SPTh. [Mn-2(CO)(10)] toluene phosphine-substituted product [Mn-2(CO)(9)(PTh3)] (10) [Mn-2)(CO)(6)(mu-PTh2)(mu-eta(1):eta(5)-C4H3S)] (11) [Mn-2(CO)(5)(PTh3)(mu-PTh2)(mu-PTh2)(mu-eta(1):eta(5)-C4H3S)] (12). Both 11 12 contain bridging thienyl ligand that bonded one manganese atom eta(5)-fashion. The molecular structures eight these complexes were established by single-crystal X-ray diffraction studies, allowing detailed analysis disposition ligands.