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

Andriy Plikhta, Alexander Pöthig, Eberhardt Herdtweck, Bernhard Rieger

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Abstract

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 PCBImP 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 [μ-OCH3Rh(COD)]2 smoothly forming the target organometallics [PCBImPPdCl][PF6] and [PCBImPRh(L)][PF6] under mild hydrogenation conditions. A more detailed study of the rhodium complexes [PCBImPRh(L)][PF6] reveals significant thermal stability of the PCBImPRh 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 PCBImPRhI complex is a sufficiently stable compound, with the potential to be applied in catalysis.

Original languageEnglish
Pages (from-to)9517-9528
Number of pages12
JournalInorganic Chemistry
Volume54
Issue number19
DOIs
StatePublished - 21 Sep 2015

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