Iridium(VII)-Corrole Terminal Carbides Should Exist as Stable Compounds.

Scalar-relativistic DFT calculations with multiple exchange-correlation functionals and large basis sets foreshadow the existence of stable iridium(VII)-corrole terminal carbide derivatives. For the parent compound Ir[Cor](C), OLYP/STO-TZ2P calculations predict a short Ir-C bond distance of 1.69 Å, a moderately domed macrocycle with no indications of ligand noninnocence, a surprisingly low electron affinity of ∼1.1 eV, and a substantial singlet-triplet gap of ∼1.8 eV. These results, and their essential invariance with respect to the choice of the exchange-correlation functional, lead us to posit that Ir(VII)-corrole terminal carbide complexes should be isolable and indefinitely stable under ambient conditions.