Toward New Organometallic Architectures: Synthesis of Carbene-Centered Rhodium and Palladium Bisphosphine Complexes. Stability and Reactivity of [PCBImPRh(L)][PF6] Pincers

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• 作者：Andriy Plikhta ; Alexander P枚thig ; Eberhardt Herdtweck ; Bernhard Rieger
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：October 5, 2015
• 年：2015
• 卷：54
• 期：19
• 页码：9517-9528
• 全文大小：631K
• ISSN：1520-510X

文摘

In this article, we report the synthesis of a tridentate carbene-centered bisphosphine ligand precursor and its complexes. The developed four-step synthetic strategy of a new PC^BImP pincer ligand represents the derivatization of benzimidazole in the first and third positions by (diphenylphosphoryl)methylene synthone, followed by phosphine deprotection and subsequent insertion of a noncoordinating anion. The obtained ligand precursor undergoes complexation, with PdCl₂ and [渭-OCH₃Rh(COD)]₂ smoothly forming the target organometallics [PC^BImPPdCl][PF₆] and [PC^BImPRh(L)][PF₆] under mild hydrogenation conditions. A more detailed study of the rhodium complexes [PC^BImPRh(L)][PF₆] reveals significant thermal stability of the PC^BImPRh moiety in the solid state as well as in solution. The chemical behavior of 1,3-bis(diphenylphosphinomethylene)benzimidazol-2-ylrhodium acetonitrile hexafluorophosphate has been screened under decarbonylation, hydrogenation, and hydroboration reaction conditions. Thus, the PC^BImPRh^I complex is a sufficiently stable compound, with the potential to be applied in catalysis.