Iron-Catalyzed H/D Exchange of Primary Silanes, Secondary Silanes, and Tertiary Siloxanes

A synthetic study into the catalytic hydrogen/deuterium (H/D) exchange of 1 degrees silanes, 2 degrees silanes, and 3 degrees siloxanes is presented, facilitated by iron-beta-diketiminato complexes (1a and 1b). Near-complete H/D exchange is observed for a variety of aryl- and alkyl-containing hydro-silanes and hydrosiloxanes. The reaction tolerates alternative hydride source pinacolborane (HBpin), with quantitative H/D exchange. A synthetic and density functional theory (DFT) investigation suggests that a monomeric iron-deuteride is responsible for the H/D exchange.

Automated summary

This paper presents a synthetic study into the catalytic hydrogen/deuterium exchange of 1 degrees silanes, 2 degrees silanes, and 3 degrees siloxanes facilitated by iron-beta-diketiminato complexes (1a and 1b). Near-complete H/D exchange is observed for various aryl- and alkyl-containing hydro-silanes and hydrosiloxanes. The reaction tolerates alternative hydride source pinacolborane (HBpin) with quantitative H/D exchange. A synthetic and density functional theory (DFT) investigation suggests that a monomeric iron-deuteride is responsible for the H/D exchange.