Heteroleptic dirhodium(II) complexes with redox-active ferrocenyl ligands: synthesis, electrochemical properties and redox-responsive chemoselectivity in carbene C-H insertion

  • Ruzhylo, Illia
  • Sournia-Saquet, Alix
  • Alain, Moreau
  • Delord, Tom
  • Manoury, Eric
  • Poli, Rinaldo
  • Labande, Agnès
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Publication date
January 2022
Publisher
Wiley

Abstract

International audienceA series of original heteroleptic dirhodium(II) complexes (4a-j) of formula Rh2(OAc)3(L), where L is a redox-active ferrocenecarboxylate ligand, has been prepared. These dirhodium(II) complexes have been characterised by NMR, mass spectrometry and cyclic voltammetry. All complexes show a quasi-reversible redox behaviour for the ferrocenyl unit. The latter can be selectively oxidised by [N(4-C6H4Br)3]+.BF4-. Four selected heteroleptic complexes 4a, 4b, 4f and 4i, have been evaluated as catalysts for the intramolecular decomposition of a diazo compound. The ratio between the aromatic substitution product 6 and the aliphatic C-H insertion product 7 increases (up to 19% increase) when using the in situ generated oxidised f...

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