Reversible Addition of
the Si–H Bond of Phenylsilane to the ScN Bond of a
Scandium Terminal Imido Complex
- Publication date
- Publisher
Abstract
The facile and reversible addition of the Si–H
bond of phenylsilane to the ScN bond of the scandium terminal
imido complex [LScNDIPP(DMAP)] (<b>1</b>; L
[MeC(N(DIPP))CHC(Me)(NCH<sub>2</sub>CH<sub>2</sub>NMe)]<sup>−</sup>, DIPP = 2,6-<sup><i>i</i></sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) is reported. The reaction gives the scandium anilido
hydride [LSc(H)(N(DIPP)(SiH<sub>2</sub>Ph))] (<b>2</b>), and
a labeling experiment shows a rapid σ-bond metathesis between
Sc–H of the formed scandium anilido hydride and Si–H
of phenylsilane during the reaction. <b>2</b> was trapped by
an insertion reaction with diphenylcarbodiimide, giving the stable
scandium anilido amidinate [LSc(N(DIPP)(SiH<sub>2</sub>Ph))(κ<sup>2</sup>(<i>N</i>,<i>N</i>′)-PhNCHNPh)]
(<b>3</b>). Furthermore, the scandium terminal imido complex
can efficiently catalyze the hydrosilylation of <i>N</i>-benzylidenepropan-1-amine. The reaction was completed within 2 h
at 50 °C with 5 mol % of catalyst loading and highly selectively
produced the monoaminosilane
