A DMRG/CASPT2 Investigation of Metallocorroles: Quantifying Ligand Noninnocence in Archetypal 3d and 4d Element Derivatives

Abstract

Hybrid density functional theory (B3LYP) and density matrix renormalization group (DMRG) theory have been used to quantitatively compare the degree of ligand noninnocence (corrole radical character) in seven archetypal metallocorroles. The seven complexes, in decreasing order of corrole noninnocent character, are Mn[Cor]Cl > Fe[Cor]Cl > Fe[Cor](NO) > Mo[Cor]Cl2 > Ru[Cor](NO) ≈ Mn[Cor]Ph ≈ Fe[Cor]Ph ≈ 0, where [Cor] refers to the unsubstituted corrolato ligand. DMRG-based second-order perturbation theory calculations have also yielded detailed excited-state energetics data on the compounds, shedding light on periodic trends involving middle transition elements. Thus, whereas the ground state of Fe[Cor](NO) (S = 0) is best described as a locally S = 1/2 {FeNO}7 unit antiferromagnetically coupled to a corrole A′ radical, the calculations confirm that Ru[Cor](NO) may be described as simply {RuNO}6-Cor3-, that is, having an innocent corrole macrocycle. Furthermore, whereas the ferromagnetically coupled S = 1{FeNO}7-Cor•2- state of Fe[Cor](NO) is only ∼17.5 kcal/mol higher than the S = 0 ground state, the analogous triplet state of Ru[Cor](NO) is higher by a far larger margin (37.4 kcal/mol) relative to the ground state. In the same vein, Mo[Cor]Cl2 exhibits an adiabatic doublet-quartet gap of 36.1 kcal/mol. The large energy gaps associated with metal-ligand spin coupling in Ru[Cor](NO) and Mo[Cor]Cl2 reflect the much greater covalent character of 4d-πinteractions relative to analogous interactions involving 3d orbitals. As far as excited-state energetics is concerned, DMRG-CASPT2 calculations provide moderate validation for hybrid density functional theory (B3LYP) for qualitative purposes, but underscore the possibility of large errors (>10 kcal/mol) in interstate energy differences.