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

Inorganic Chemistry
Nicolaas P. van Leest, Bas de Bruin

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 ([CoIII(TPP)(•CHCO2Et)]) and mononitrene ([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 electron paramagnetic resonance analysis and spin counting, paramagnetic molar susceptibility determination, and NEVPT2-CASSCF calculations, we report that the cobalt porphyrin bisnitrene complex ([CoIII(TPP•)(•NN...Continue Reading

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