Synthesis and Reactivity of Discrete Calcium Imides

Protonolysis of dibenzylcalcium with triphenylsilylamine affords a thf‐coordinated tetrametallic calcium imide with a heterocuboid core structure. The use of calcium bis(tetramethylaluminate) as a precursor for tandem salt metathesis/protonolysis reactions with alkali metal amides of 2,6‐diisopropylaniline and triphenylsilylamine provides access to Lewis acid stabilized monocalcium imides of the type [(thf) 4 Ca(μ 2 ‐NR)(μ 2 ‐Me)AlMe 2 ]. Treatment of [(thf) 4 Ca(μ 2 ‐NSiPh 3 )(μ 2 ‐Me)AlMe 2 ] with phenylsilane results in H−Si addition across the Ca−N imido bond, producing a homoleptic calcium amidoaluminate complex and putative CaH 2 whereas reaction with phenylacetylene leads to protonation of an AlMe moiety to yield the dimeric complex [(thf)Ca{NSiPh 3 }{AlMe 2 (CCPh)}] 2 .