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, mono- and bis-nitrene radical complexes coordinated to [Co(TPP)] (TPP = tetraphenylporphyrin) have previously been investigat-ed with a variety of experimental techniques and supporting (single-reference) DFT calculations that indicated doublet (S = ½) ground states for all three species. In this contribution we revisit their electronic structures with multireference NEVPT2-CASSCF calculations to investigate possible multireference contributions to the ground state wavefunctions. The carbene ([CoIII(TPP)(•CHCO2Et)]) and mono-nitrene ([CoIII(TPP)(•NNs)]) radical complexes were confirmed to have uncomplicated doublet ground states, although a higher carbene or nitrene radical character and a lower Co‒C/N bond order was found in the NEVPT2-CASSCF calculations. Supported by EPR analysis and spin counting, paramagnetic molar susceptibility determination and NEVPT2-CASSCF calculations, we report that the cobalt-porphyrin bis-nitrene complex ([CoIII(TPP•)(•NNs)2]) has a quartet (S = 3/2) spin ground state, with a thermally assessable multireference & multideterminant ‘broken-symmetry’ doublet spin excited state. A spin flip on the porphyrin-centered unpaired electron allows for interconversion between the quartet and broken-symmetry doublet spin states, with an approximate 10- and 200-fold higher Boltzmann population of the quartet at room tempera-ture or 10 K, respectively.