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

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.