Bisphosphine monoxide complexes of transition metals have been used as catalysts for various organic transformations. The synthesis of these complexes starts typically with the preparation of the bisphosphine monoxide ligand, which is combined with the metal precursor complex. Bisphosphine monoxides are prepared either by combination of two fragments of molecules or by selective oxidation of a parent bisphosphine molecule. Options have been explored to use the redox properties of a given transition metal (AuIII, RhIII) to combine the two reaction steps: (i) the selective oxidation of a bisphosphine and (ii) the complexation of the ligand at the metal center in a one-pot synthesis by reaction of MCl3 ● nH2O (M = Au, Rh) and the bisphosphine (1,2-bis(diphenylphosphino)benzene, dppbz). The formation of [Au(dppbzO)Cl] was discovered in an unexpected reaction involving the reduction of the gold(III) center in the presence of water, which served as oxygen source. The reaction of RhCl3 ● nH2O with dppbz in acetonitrile under similar conditions lead to the formation of fac-[RhCl3(dppbz)(CH3CN)]. Under different reaction conditions, in the presence of PPh3 in THF, mer-[RhCl3(dppbzO)(thf)] was formed. The formation of the rhodium(III) bisphosphine monoxide complex involves presumably oxygen transfer mediated by PPh3.

Expected and unexpected one-pot synthesis of bisphosphine monoxide complexes of late transition metals

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.