Ligand Redox Noninnocence in [Co^III(TAML)]^0/- Complexes Affects Nitrene Formation.

ABSTRACT: The redox noninnocence of the TAML scaffold in cobalt-TAML (tetra-amido macrocyclic ligand) complexes has been under debate since 2006. In this work, we demonstrate with a variety of spectroscopic measurements that the TAML backbone in the anionic complex [Co^III(TAML^red)]^- is truly redox noninnocent and that one-electron oxidation affords [Co^III(TAML^sq)]. Multireference (CASSCF) calculations show that the electronic structure of [Co^III(TAML^sq)] is best described as an intermediate spin (S = 1) cobalt(III) center that is antiferromagnetically coupled to a ligand-centered radical, affording an overa

SUBMITTER: van Leest NP 

PROVIDER: S-EPMC6956250 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature