Remote Oxidative Activation of a [Cp*Rh] Monohydride.

ABSTRACT: Half-sandwich rhodium monohydrides are often proposed as intermediates in catalysis, but little is known regarding the redox-induced reactivity accessible to these species. Herein, the bis(diphenylphosphino)ferrocene (dppf) ligand has been used to explore the reactivity that can be induced when a [Cp*Rh] monohydride undergoes remote (dppf-centered) oxidation by 1e^- . Chemical and electrochemical studies show that one-electron redox chemistry is accessible to Cp*Rh(dppf), including a unique quasi-reversible Rh^II/I process at -0.96 V vs. ferrocenium/ferrocene (Fc^+/0 ). This redox manifold was confirmed by isolation of an uncommon Rh^II species, [Cp*Rh(dppf)]⁺ , that was characterized by electron paramagnetic resonance (EPR) spectroscopy.

SUBMITTER: Boyd EA 

PROVIDER: S-EPMC8891045 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature