Adams Richard D, Captain Burjor, Trufan Eszter, Zhu Lei
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, USA.
J Am Chem Soc. 2007 Jun 20;129(24):7545-56. doi: 10.1021/ja070617h. Epub 2007 May 26.
The compounds HM(CO)4SnPh3, M = Os (10), Ru (11) are activated in the presence of Pt(PBut3)2 and Pd(PBu(t)3)2 toward the insertion of PhC2H into the M-H bond. The compounds PtOs(CO)4(SnPh3)(PBu(t)3)[mu-HCC(H)Ph], 12, and PtOs(CO)4(SnPh3)(PBu(t)3)[mu-H2CCPh], 13, were obtained from the reaction of 10 with PhC2H in the presence of Pt(PBu(t)3)2. Compounds 12 and 13 are isomers containing alkenyl ligands formed by the insertion of the PhC2H molecule into the Os-H bond at both the substituted and unsubstituted carbon atoms of the alkyne. Both compounds contain a Pt(PBu(t)3) group that is bonded to the osmium atom and a bridging alkenyl ligand that is pi-bonded to the osmium atom. The reaction of 11 with PhC2H in the presence of Pt(PBu(t)3)2 yielded the products PtRu(CO)4(SnPh3)(PBu(t)3)[mu-HC2(H)Ph], 14, and PtRu(CO)4(SnPh3)(PBut3)[mu-H2C2Ph], 15, which are also isomers similar to 12 and 13. The reaction of 11 with PhC2H in the presence of Pd(PBu(t)3)2 yielded the product PdRu(CO)4(SnPh3)(PBu(t)3)[mu-H2C2Ph], 16. Compound 16 contains a Pd(PBu(t)3) group bonded to the ruthenium atom and a bridging H2C2Ph ligand that is pi-bonded to the palladium atom. Compound 10 reacted with Pt(PBu(t)3)2 in the absence of PhC2H to yield the compound PtOs(CO)4(SnPh3)(PBu(t)3)(mu-H), 17. Compound 17 is a Pt(PBu(t)3) adduct of 10. It contains a Pt-Os bond with a bridging hydrido ligand. Compound 17 reacted with PhC2H to yield 12. Compound 12 reacted with PhC2H to yield the compound PtOs(CO)3(SnPh3)(PBu(t)3)[mu-HCC(Ph)C(H)C(H)Ph], 18. Compound 18 contains a bridging 2,4-diphenylbutadienyl ligand, HCC(Ph)C(H)C(H)Ph, that is pi-bonded to the osmium atom and sigma-bonded to the platinum atom. Fenkse-Hall molecular orbitals of 17 were calculated. The LUMO of 17 exhibits an empty orbital on the platinum atom that appears to be the most likely site for PhC2H addition prior to its insertion into the Os-H bond.
化合物HM(CO)₄SnPh₃（M = Os (10)，Ru (11)）在Pt(PBut₃)₂和Pd(PBu(t)₃)₂存在下被活化，促使PhC₂H插入M - H键。化合物PtOs(CO)₄(SnPh₃)(PBu(t)₃)[μ - HCC(H)Ph]，12，和PtOs(CO)₄(SnPh₃)(PBu(t)₃)[μ - H₂CCPh]，13，是由10与PhC₂H在Pt(PBu(t)₃)₂存在下反应得到的。化合物12和13是异构体，含有通过PhC₂H分子插入炔烃取代和未取代碳原子处的Os - H键而形成的烯基配体。两种化合物都含有一个与锇原子键合的Pt(PBu(t)₃)基团和一个与锇原子形成π键的桥连烯基配体。11与PhC₂H在Pt(PBu(t)₃)₂存在下反应生成产物PtRu(CO)₄(SnPh₃)(PBu(t)₃)[μ - HC₂(H)Ph]，14，和PtRu(CO)₄(SnPh₃)(PBut₃)[μ - H₂C₂Ph]，15它们也是与12和13类似的异构体。11与PhC₂H在Pd(PBu(t)₃)₂存在下反应生成产物PdRu(CO)₄(SnPh₃)(PBu(t)₃)[μ - H₂C₂Ph]，16。化合物16含有一个与钌原子键合的Pd(PBu(t)₃)基团和一个与钯原子形成π键的桥连H₂C₂Ph配体。化合物10在没有PhC₂H的情况下与Pt(PBu(t)₃)₂反应生成化合物PtOs(CO)₄(SnPh₃)(PBu(t)₃)(μ - H)，17。化合物17是10的Pt(PBu(t)₃)加合物。它含有一个带有桥连氢化物配体的Pt - Os键。化合物17与PhC₂H反应生成12。化合物12与PhC₂H反应生成化合物PtOs(CO)₃(SnPh₃)(PBu(t)₃)[μ - HCC(Ph)C(H)C(H)Ph]，18。化合物18含有一个桥连的2,4 - 二苯基丁二烯基配体，HCC(Ph)C(H)C(H)Ph，它与锇原子形成π键并与铂原子形成σ键。计算了17的Fenkse - Hall分子轨道。17的最低未占分子轨道在铂原子上呈现一个空轨道，这似乎是PhC₂H在插入Os - H键之前最可能加成的位点。
