CH and PC bond activations of PMe2Ph ligands by an octahedral Ru6 cluster
摘要:
The compound Ru-6(CO)(15)(PMe2Ph)(2)(mu(6)-C) (1) was obtained from the reaction of Ru-6(CO)(17)(mu(6)-C) with PMe2-Ph. Compound 1 exists in solution as a mixture of two slowly interconverting isomers. It is decarbonylated by treatment with Me3NO.2H(2)O to yield two new products Ru-6(CO)(13)(mu-PMe2)(mu(3)-eta(3)-Me2PC6H4)(mu(6)-C) (2) and Ru-6(CO)(14)(PMe2Ph)(mu-eta(2)-MePhPCH2)(mu(6)-C)(mu-H) (3). Compound 2 is also obtained from I by thermal decarbonylation at 127 degreesC together with two additional compounds: Ru-6(CO)(14)(mu-PMe2)(mu-eta(2)-MePhPCH2)(mu(6)-C) (4) and Ru-6(CO)(12)(mu-PMe2)(2)(mu(3)-eta(2)-C6H4)(mu(6)-C) (5). Compound 2 reacts reversibly with CO to form the CO adduct Ru-6(CO)(14)(mu-PMe2)(mu-eta(2)-Me2PC6H4)(mu(6)-C) (6). The structures of compounds 1-6 were established crystallographically. All contain octahedral RU6 Clusters with a carbido ligand in the center. Except for 1, all contain phosphine ligands in various stages of degradation. Compound 2 contains one bridging PMe2 ligand formed by loss of a phenyl ring from a PMe2Ph ligand and a bridging eta(3)-Me2PC6H4 ligand formed by ortho-metallation of the phenyl ring of the second PMe2Ph ligand. Compound 3 contains a bridging eta(2)-MePhPCH2 ligand formed by metallation of one of the methyl groups of a PMe2Ph ligand. Compound 4 contains a bridging PMe2 and a bridging eta(2)-MePhPCH2 ligand. Compound 5 contains two bridging PMe2 ligands and a bridging (mu(3)-eta(2)-C6H4) benzyne ligand fromed by cleavage of a phenyl ring from one of the PMe2Ph ligands. Compound 6 contains one bridging PMe2 ligand and a bridging eta(2)-MePC6H4 ligand formed by ortho-metallation of the phenyl ring of one of the PMe2Ph ligands. (C) 2002 Elsevier Science BY. All rights reserved.
CH and PC bond activations of PMe2Ph ligands by an octahedral Ru6 cluster
摘要:
The compound Ru-6(CO)(15)(PMe2Ph)(2)(mu(6)-C) (1) was obtained from the reaction of Ru-6(CO)(17)(mu(6)-C) with PMe2-Ph. Compound 1 exists in solution as a mixture of two slowly interconverting isomers. It is decarbonylated by treatment with Me3NO.2H(2)O to yield two new products Ru-6(CO)(13)(mu-PMe2)(mu(3)-eta(3)-Me2PC6H4)(mu(6)-C) (2) and Ru-6(CO)(14)(PMe2Ph)(mu-eta(2)-MePhPCH2)(mu(6)-C)(mu-H) (3). Compound 2 is also obtained from I by thermal decarbonylation at 127 degreesC together with two additional compounds: Ru-6(CO)(14)(mu-PMe2)(mu-eta(2)-MePhPCH2)(mu(6)-C) (4) and Ru-6(CO)(12)(mu-PMe2)(2)(mu(3)-eta(2)-C6H4)(mu(6)-C) (5). Compound 2 reacts reversibly with CO to form the CO adduct Ru-6(CO)(14)(mu-PMe2)(mu-eta(2)-Me2PC6H4)(mu(6)-C) (6). The structures of compounds 1-6 were established crystallographically. All contain octahedral RU6 Clusters with a carbido ligand in the center. Except for 1, all contain phosphine ligands in various stages of degradation. Compound 2 contains one bridging PMe2 ligand formed by loss of a phenyl ring from a PMe2Ph ligand and a bridging eta(3)-Me2PC6H4 ligand formed by ortho-metallation of the phenyl ring of the second PMe2Ph ligand. Compound 3 contains a bridging eta(2)-MePhPCH2 ligand formed by metallation of one of the methyl groups of a PMe2Ph ligand. Compound 4 contains a bridging PMe2 and a bridging eta(2)-MePhPCH2 ligand. Compound 5 contains two bridging PMe2 ligands and a bridging (mu(3)-eta(2)-C6H4) benzyne ligand fromed by cleavage of a phenyl ring from one of the PMe2Ph ligands. Compound 6 contains one bridging PMe2 ligand and a bridging eta(2)-MePC6H4 ligand formed by ortho-metallation of the phenyl ring of one of the PMe2Ph ligands. (C) 2002 Elsevier Science BY. All rights reserved.