Synthesis, Characterization and Structural Properties of Some Heterobimetallic Carbonyl Clusters Derived from Diethynylsilane and Diethynyldisilane Ligands

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• 作者：Chun-Kin Wong (1)
  Guo-Liang Lu (2)
  Cheuk-Lam Ho (1)
  Wai-Yeung Wong (1) rwywong@hkbu.edu.hk
  Zhenyang Lin (1)
• 关键词：Alkyne &#8211 ; Cobalt &#8211 ; Mixed ; metal cluster &#8211 ; Osmium &#8211 ; Ruthenium
• 刊名：Journal of Cluster Science
• 出版年：2012
• 出版时间：September 2012
• 年：2012
• 卷：23
• 期：3
• 页码：885-900
• 全文大小：535.5 KB
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• 作者单位：1. Department of Chemistry, Hong Kong Baptist University, Waterloo Road, Kowloon Tong, Hong Kong, People鈥檚 Republic of China2. Auckland Cancer Society Research Centre, The University of Auckland, Private Bag 92019, Auckland, 1142 New Zealand
• ISSN：1572-8862

文摘

We report the synthesis of some heterobimetallic carbonyl clusters of groups 8 and 9 derived from diethynylsilane and diethynyldisilane ligands. The triosmium carbonyl clusters containing a pendant acetylene unit [(μ-CO)Os₃(CO)₉(μ₃-η2-HC≡C-E-C≡CH)] [E = Si(CH₃)₂, Si(CH₃)₂–Si(CH₃)₂ and SiPh₂] were prepared and subsequently used for mixed-metal cluster formation. New diyne complexes of the type [{(μ-CO)Os₃(CO)₉}{Co₂(CO)₆}(μ₃-η2:η2-diyne)] and [{(μ-CO)Os₃(CO)₉}{(μ-H)Ru₃(CO)₉}(μ₃-η2:μ₃-η2, η2-diyne)] [diyne = HC≡CSi(CH₃)₂C≡CH, HC≡CSi(CH₃)₂–Si(CH₃)₂C≡CH or HC≡CSi(Ph)₂C≡CH] have been prepared in good yields from the reaction of [(μ-CO)Os₃(CO)₉(μ₃-η2-HC≡C-E-C≡CH)] with a molar equivalent of [Co₂(CO)₈] and [Ru₃(CO)₁₂], respectively. All the new heterobimetallic compounds have been characterized by IR and 1H NMR spectroscopy and mass spectrometry. The X-ray crystal structures and computational analyses based on density functional theory of these three molecules have been studied. Structurally, the dicobalt species adopts a pseudo-tetrahedral Co₂C₂ core with the alkyne bond which lies essentially perpendicular to the Co–Co vector. For the mixed osmium–ruthenium analogue, the hexanuclear carbonyl cluster consist of two trinuclear metal cores with the μ₃-(η2-||) bonding mode for the acetylene group in the former case and the μ₃-η2, η2 bonding mode in the latter one.