The Reaction of mu-eta~2:eta~2-Peroxo-and Bis(mu-oxo)dicopper Complexes with Flavonol

摘要

The[Cu_2(mu-O)_2]~(2+)and[Cu_2(mu-eta~2:eta~2-O)_2]~(2+)motifs with coordinated N,N,N-tribenzyl-l,4,7-triazacyclononane and N,N,N-triisopropyl-l,4,7-triazacyclononane auxiliary ligands in their reaction with flavonol do not lead to ring scission products of the heterocycle,but the formation of the corresponding(flavonolato)copper(II)complexes[Cu(fla)(Bz-TAC)]ClO_4 and[Cu(fla)(iPr-TAC)]ClO_4.The subsequent oxygenolysis of the coordinated flavonolate ligand leads to OMICRON-benzoylsalicylate at elevated temperature,resulting in the enzyme mimicking products[Cu(O-bs)(Bz-TAC)]ClO_4,[Cu(O-bs)(iPr-TAC)]-C1O_4)as well as carbon monoxide.The X-ray structures of[Cu(fla)(Bz-TAC)]ClO_4,[Cu(O-bs)(Bz-TAC)]ClO_4,and[Cu(O-bs)(iPr-TAC)]ClO_4)are presented.