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• 作者：Richard D. Adams ; Erin M. Boswell ; Michael B. Hall ; Xinzheng Yang
• 刊名：Organometallics
• 出版年：2008
• 出版时间：October 13, 2008
• 年：2008
• 卷：27
• 期：19
• 页码：4938-4947
• 全文大小：535K
• 年卷期：v.27,no.19(October 13, 2008)
• ISSN：1520-6041

文摘

Reactions of the unsaturated mixed metal cluster complex PtOs₃(CO)₇(PBu^t₃)(μ-PBu^t₂)(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(PBu^t₃)(μ-PBu^t₂)(μ₄-CHCMeCH)(μ-H)(H), 2. A computational analysis shows that the hydrogen addition occurs by oxidative addition at the electronically unsaturated platinum atom and passes through two unstable intermediates before giving the final product 2. Compound 1 reacts with HGePh₃ at the Ge−H bond to form the complex PtOs₃(CO)₇(PBu^t₃)(μ-PBu^t₂)(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 PBu^t₃ ligand to give the compound Os₃(CO)₇(μ-PBu^t₂)[μ₃-η⁵-CHCMeC(H)CCPhH], 4. In the process, the PhC₂H molecule became bonded to the CHCMeCH ligand in 1 and its hydrogen atom was shifted to the phenyl-substituted carbon atom to form a triply bridging CHCMeC(H)CCPhH ligand. All of the products were characterized by single-crystal X-ray diffraction analyses.