Deoxygenation of Nitroxyl Radicals by Oxorhenium(V) Complexes with Redox-Active Ligands

作者：Lippert Cameron A; Soper Jake D^*

来源：Inorganic Chemistry, 2010, 49(8): 3682-3684.

DOI：10.1021/ic9024684

Five-coordinate oxorhenium(V) anions with redox-active catecholate ligands deoxygenate stable nitroxyl radicals, including TEMPO(center dot), to afford dioxorhenium(VII) complexes and aminyl radical-derived products. A structural homologue with redox-inert oxalate ligands does not react with TEMPO(center dot). Redox-active ligands are proposed to lower the kinetic barrier to TEMPO deoxygenation by giving access to 1e(-) redox steps that are crucial for the formation and stabilization of intermediate species.

• 出版日期2010-4-19