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

Abstract

Scalar-relativistic DFT calculations with multiple exchangecorrelation 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 exchangecorrelation functional, lead us to posit that Ir(VII)−corrole terminal carbide complexes should be isolable and indefinitely stable under ambient conditions.