Revisiting the Electronic Structure of Cobalt Porphyrin Nitrene and Carbene Radicals with NEVPT2-CASSCF Calculations: Doublet versus Quartet Ground States.

ABSTRACT: Cobalt porphyrin complexes are established catalysts for carbene and nitrene radical group-transfer reactions. The key carbene and mono- and bisnitrene radical complexes coordinated to [Co(TPP)] (TPP = tetraphenylporphyrin) have previously been investigated with a variety of experimental techniques and supporting (single-reference) density functional theory (DFT) calculations that indicated doublet (S = ¹/₂) ground states for all three species. In this contribution, we revisit their electronic structures with multireference N-electron valence state perturbation theory (NEVPT2)-complete-active-space self-consistent-field (CASSCF) calculations to investigate possible multireference contributions to the ground-state wave functions. The carbene ([Co^I

SUBMITTER: van Leest NP 

PROVIDER: S-EPMC8220492 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature