Unique Ligand-Radical Character of an Activated Cobalt Salen Catalyst That Is Generated by Aerobic Oxidation of a Cobalt(II) Salen Complex

The Co­(salen)­(X) complex, where salen is chiral N,N′-bis­(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine and X is an external axial ligand, has been widely utilized as a versatile catalyst. The Co­(salen)­(X) complex is a stable solid that has been conventionally described as a CoIII(salen)­(X) complex. Recent theoretical calculations raised a new proposal that the Co­(salen)­(H2O)­(SbF6) complex contains appreciable contribution from a CoII(salen•+) electronic structure (Kochem, A.; Kanso, H.; Baptiste, B.; Arora, H.; Philouze, C.; Jarjayes, O.; Vezin, H.; Luneau, D.; Orio, M.; Thomas, F. Inorg. Chem. 2012, 51, 10557–10571), while other theoretical calculations for Co­(salen)­(Cl) indicated a triplet CoIII(salen) electronic structure (Kemper, S.; Hrobárik, P.; Kaupp, M.; Schlörer, N. E. J. Am. Chem. Soc. 2009, 131, 4172–4173). However, there have been no experimental data to evaluate these theoretical proposals. We herein report key experimental data on the electronic structure of the Co­(salen)­(X) complex (X = CF3SO3–, SbF6–, and p-MeC6H4SO3–). The X-ray crystallography shows that Co­(salen)­(OTf) has a square-planar N2O2 equatorial coordination sphere with OTf as an elongated external axial ligand. Magnetic susceptibility data indicate that Co­(salen)­(OTf) complexes belong to the S = 1 spin system. 1H NMR measurements provide convincing evidence for the CoII(salen•+)­(X) character, which is estimated to be about 40% in addition to 60% CoIII(salen)­(X) character. The CH2Cl2 solution of Co­(salen)­(X) shows an intense near-IR absorption, which is assigned as overlapped transitions from a ligand-to-metal charge transfer in CoIII(salen)­(X) and a ligand-to-ligand charge transfer in CoII(salen•+)­(X). The present experimental study establishes that the electronic structure of Co­(salen)­(X) contains both CoII(salen•+)­(X) and CoIII(salen)­(X) character.