Electronic structure of high-valent transition metal corrolazine complexes. The young and innocent?

Abstract

This is a first quantum chemical study of corrolazine complexes. DFT calculations suggest that despite their extremely contracted central cavities, compared with porphyrins, a variety of corrolazine complexes may be expected to exist as stable compounds. The calculations also indicate that corrolazine complexes may be regarded as strongly electron-deficient analogues of corrole complexes. Thus, the calculated valence ionization potentials of P(V) and Cu(III) corrolazine derivatives are dramatically higher than those of analogous corrole derivatives. In addition, DFT calculations on Fe(IV) and Mn(IV) corrole and corrolazine derivatives suggest that compared with the often noninnocent corrole ligands, corrolazines are electronically more innocent and stabilize "purer" high-valent states of transition metal ions.