Tetrapalladium Complex with Bridging Germylene Ligands. Structural Change of the Planar Pd4Ge3 Core

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• 作者：Makoto Tanabe ; Naoko Ishikawa ; Mai Chiba ; Tomohito Ide ; Kohtaro Osakada ; Tomoaki Tanase
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：November 23, 2011
• 年：2011
• 卷：133
• 期：46
• 页码：18598-18601
• 全文大小：829K
• 年卷期：v.133,no.46(November 23, 2011)
• ISSN：1520-5126

文摘

A complex with a planar hexagonal Pd₄Ge₃ core, [Pd{Pd(dmpe)}₃(渭₃-GePh₂)₃], was synthesized and characterized by X-ray and NMR measurements as well as by DFT calculations. 4-tert-Butylbenzenethiol converted the Pd₄ complex into a hexapalladium complex, [{Pd₃(渭-GePh₂)₂(渭-H)(渭₃-GePh₂(SC₆H₄^tBu-4))}₂(渭-dmpe)], composed of two Pd₃Ge₃ units bridged by a dmpe ligand. The addition of CuI or AgI to the Pd₄ complex yielded [Pd(渭-MI){Pd(dmpe)}₃(渭₃-GePh₂)₃ ] (M = Cu, Ag), in which Cu or Ag bridges a Pd鈥揚d bond of the Pd₄Ge₃ core. The CuI adducts in solution undergo a pivot motion of the CuI on the surface of the Pd₄Ge₃ plane on the NMR time scale.