[Organometallics] The activation of hydrogen and related small molecules by the unsaturated cluster complex PtOs3(CO)7(PBut3)(µ-PBut2)(µ4-CHCMeCH)

Authors:  Richard D. Adams,*†  Erin M. Boswell,†  Michael B. Hall,*‡  and   Xinzheng Yang‡
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, and Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255

Web Release Date: September 5, 2008

DOI: 10.1021/om800467v

Abstract: Reactions of the unsaturated mixed metal cluster complex PtOs3(CO)7(PBut3)(μ-PBut2)(μ4-CHCMeCH), 1, with hydrogen, HGePh3, and PhC2H have been investigated. Compound 1 reacts reversibly with hydrogen at room temperature to yield the dihydrido complex PtOs3(CO)7(PBut3)(μ-PBut2)(μ4-CHCMeCH)(μ-H)(H), 2.A computational analysis shows that the hydrogen addition occurs byoxidative addition at the electronically unsaturated platinum atom andpasses through two unstable intermediates before giving the finalproduct 2. Compound 1 reacts with HGePh3 at the Ge−H bond to form the complex PtOs3(CO)7(PBut3)(μ-PBut2)(μ4-CHCMeCH)(GePh3)(μ-H), 3, but in this reaction the HGePh3 addition occurred at one of the osmium atoms and a CO ligand was shifted to the platinum atom. Compound 1 reacts with PhC2H by loss of the platinum atom and the PBut3 ligand to give the compound Os3(CO)7(μ-PBut2)[μ3-η5-CHCMeC(H)CCPhH], 4. In the process, the PhC2H molecule became bonded to the CHCMeCH ligand in 1and its hydrogen atom was shifted to the phenyl-substituted carbon atomto form a triply bridging CHCMeC(H)CCPhH ligand. All of the productswere characterized by single-crystal X-ray diffraction analyses.

Link: http://dx.doi.org/10.1021/om800467v

Remards: 还是与Richard Adams组的合作，他们的实验发现不饱和金属团簇化合物1可以与H2、PhCCH以及PH3GeH反应生成新的化合物，其中在室温下与H2的反应是可逆的。我们则通过计算解释了它们的反应机理。按Richard Adams的习惯，作者以Last name排序。