Redox-active ligand based Mn()-catalyst for hydrosilylative ester reduction

Herein a Mn( i ) catalyst bearing a redox-active phenalenyl (PLY) based ligand is reported for the efficient hydrosilylation of esters to alcohols using the inexpensive silane source polymethylhydrosiloxane (PMHS) under mild conditions. Mechanistic investigations suggest a strong ligand-metal cooperation where a ligand-based single electron transfer (SET) process initiates the reaction through Si-H bond activation. A redox-active ligand-based Mn( i ) catalyst initiates a single electron transfer (SET) to split the Si-H bond of PMHS leading to ester hydrosilylation under mild conditions.