Electrifying Hydroformylation Catalysts Exposes Voltage-Driven C-C Bond Formation.

Electrochemical reactions can access a significant range of driving forces under operationally mild conditions and are thus envisioned to play a key role in decarbonizing chemical manufacturing. However, many reactions with well-established thermochemical precedents remain difficult to achieve electrochemically. For example, hydroformylation (thermo-HFN) is an industrially important reaction that couples olefins and carbon monoxide (CO) to make aldehydes.

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

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 process at -0.