A Stable Aminyl Radical Coordinated to Cobalt

作者：Rodriguez Lugo Rafael E; de Bruin Bas^*; Trincado Monica^*; Grutzmacher Hansjorg^*

来源：Chemistry - A European Journal, 2017, 23(28): 6795-6802.

DOI：10.1002/chem.201605624

• aminyl
• cobalt complexes
• density functional calculations
• radical
• spin density

A family of cobalt complexes bearing the trop(2)NH [bis(5-H-dibenzo[a,d]cyclohepten-5-yl)-amine] and 2,2'-bpy (2,2'-bipyridine) chelate ligands were prepared and fully characterized. The compounds [Co(trop(2)N)(bpy)], [Co(trop(2)NH)(bpy)](+), and [Co(trop(2)N)(bpy)](+) are cobalt complexes interrelated by one-electron redox processes and/or proton transfer. Two limiting resonance structures can be used to describe the paramagnetic complex [Co(trop(2)N)(bpy)](+): [Co-II(trop(2)N(-))(bpy)](+) (Co-II amido) and [Co-I(trop(2)N)(bpy)](+) (Co-I-aminyl radical). Structural data, DFT calculations, and reactivity toward H-abstraction indicate a slightly higher contribution of the aminyl radical form to the ground state of [Co(trop(2)N)(bpy)](+). The results described here complete the series of Group9 metal aminyl radical complexes bearing the diolefin amine ligand trop(2)NH.

• 出版日期2017-5