[La{N(SiMe<sub>3</sub>)<sub>2</sub>}<sub>3</sub>THF<sub>2</sub>] (<b>1</b>) is an effective precatalyst
for the heterodehydrocoupling
of silanes and amines. Coupling of primary and secondary amines with
aryl silanes was achieved with a loading of 0.8 mol % of [La{N(SiMe<sub>3</sub>)<sub>2</sub>}<sub>3</sub>THF<sub>2</sub>]. With primary amines,
generation of tertiary and sometimes quaternary silamines was facile,
often requiring only a few hours to reach completion, including new
silamines Ph<sub>3</sub>Si(<sup><i>n</i></sup>PrNH) and
Ph<sub>3</sub>Si(<sup><i>i</i></sup>PrNH). Secondary amines
were also available for heterodehydrocoupling, though they generally
required longer reaction times and, in some instances, higher reaction
temperatures. This work expands upon the utility of <i>f</i>-block complexes in heterodehydrocoupling catalysis
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