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° silanes, 2° silanes, and 3° siloxanes is presented, facilitated by iron-β-diketiminato complexes ( 1a and 1b ). Near-complete H/D exchange is observed for a variety of aryl- and alkyl-containing hydrosilanes 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.