Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus de Montilivi, E-17071 Girona, Spain ; Catalan Institute for Water Research (ICRA), H2O Building, Scientific and Technological Park of the University of Girona, Emili Grahit 101, E-17003 Girona, Spain.
Beilstein J Org Chem. 2013 Mar 20;9:585-93. doi: 10.3762/bjoc.9.63. Print 2013.
In this work we analyze the whole molecular mechanism for intramolecular aromatic hydroxylation through O2 activation by a Schiff hexaazamacrocyclic dicopper(I) complex, Cu(I) 2(bsH2m). Assisted by DFT calculations, we unravel the reaction pathway for the overall intramolecular aromatic hydroxylation, i.e., from the initial O2 reaction with the dicopper(I) species to first form a Cu(I)Cu(II)-superoxo species, the subsequent reaction with the second Cu(I) center to form a μ-η(2):η(2)-peroxo-Cu(II) 2 intermediate, the concerted peroxide O-O bond cleavage and C-O bond formation, followed finally by a proton transfer to an alpha aromatic carbon that immediately yields the product Cu(II) 2(bsH2m-O)(μ-OH).
在这项工作中，我们通过席夫碱六氮大环二铜（I）配合物[Cu（I）2（bsH2m）]（2+）对 O2 的活化来分析分子内芳香族羟化的整个分子机制。借助 DFT 计算，我们揭示了整个分子内芳香族羟化的反应途径，即从最初的 O2 与二铜（I）物种的反应开始，形成 Cu（I）Cu（II）-过氧物种，然后与第二个 Cu（I）中心反应形成 μ-η（2）：η（2）-过氧-Cu（II）2 中间体，协同过氧化物 O-O 键断裂和 C-O 键形成，最后质子转移到α芳基碳上，立即生成产物[Cu（II）2（bsH2m-O）（μ-OH）]（2+）。
