Harnessing redox-active ligands for low-barrier radical addition at oxorhenium complexes.

摘要: The addition of an [X]+ electrophile to the five-coordinate oxorhenium(V) anion [ReV(O)(apPh)2]− {[apPh]2– = 2,4-di-tert-butyl-6-(phenylamido)phenolate} gives new products containing Re–X bonds. bond-forming reaction is analogous oxo transfer in that both are 2e– redox processes, but electronic structures different. Whereas yields a closed-shell [ReVII(O)2(apPh)2]− product metal oxidation, [Cl]+ diradical ReVI(O)(apPh)(isqPh)Cl ([isqPh]•– 2,4-di-tert-butyl-6-(phenylimino)semiquinonate) with 1e– Re d orbital and on redox-active ligand. differences structure ascribed π basicity [O]2– Cl– ligands. observation ligand radicals ReVI(O)(apPh)(isqPh)X provides experimental support for capacity ligands deliver electrons other reactions at [ReV(O)(apPh)2]−, including radical additions ...