Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity.

Bimetallic (Et4N)2[Co2(L)2], (Et4N)2[1] (where (L)(3-) = (N(o-PhNC(O)(i)Pr)2)(3-)) reacts with 2 equiv of O2 to form the monometallic species (Et4N)[Co(L)O2], (Et4N)[3]. A crystallographically characterized analog (Et4N)2[Co(L)CN], (Et4N)2[2], gives insight into the structure of [3](1-). Magnetic measurements indicate [2](2-) to be an unusual high-spin Co(II)-cyano species (S = 3/2), while IR, EXAFS, and EPR spectroscopies indicate [3](1-) to be an end-on superoxide complex with an S = 1/2 ground state. By X-ray spectroscopy and calculations, [3](1-) features a high-spin Co(II) center; the net S = 1/2 spin state arises after the Co electrons couple to both the O2(•-) and the aminyl radical on redox non-innocent (L(•))(2-). Dianion [1](2-) shows both nucleophilic and electrophilic catalytic reactivity upon activation of O2 due to the presence of both a high-energy, filled O2(-) π* orbital and an empty low-lying O2(-) π* orbital in [3](1-).