Electronic Structure of Gallium, Copper, and Nickel Complexes of Corrole. High-Valent Transition Metal Centers versus Noninnocent Ligands

摘要: Using regular nonlocal density functional theory (DFT) as well combined DFT and configuration interaction calculations, we have carried out a first theoretical study of the electronic structure metallocorroles. The valence orbital energy spectra calculated absorption spectrum (Cor)Ga (Cor3- = corrolato), prototype non-transition-metal corrole, are qualitatively similar to those metalloporphyrin such zinc porphyrin. “four-orbital model” holds for corroles. a2 b1 HOMOs crude analogues well-known a1u a2u porphyrin HOMOs, respectively. Thus, in case porphyrins, there two nearly equienergetic π-cation radical states also appears provide good description stabilization high-valent transition-metal centers ligand noninnocence, intertwined central themes metallocorrole chemistry. ground state (Cor)Cu is diamagnetic d8 Cu(III) state, with Cu(II) π-cati...