Heavy Alkaline Earth Cyclic (Alkyl)(Amino)Carbene Complexes Supported by Aryl–Silyl Amides

A series of 8 trigonal planar, heavy alkaline earth (AE = Ca–Ba) metal complexes containing cyclic (alkyl)(amino)carbene (CAAC) ligands were prepared from AE bis(amide) species. Complexation can be achieved by first generating the free carbene in situ or by direct addition of the free carbene, with the former route giving rise to unexpected mixed-amide AE complexes. The frontier molecular orbitals of the highly equatorial, 3-coordinate AE-CAAC species were also probed computationally, revealing the lowest unoccupied molecular orbital (LUMO) consisting predominantly of the π* system located on the carbene ligand.