Aromatic hydroxylation reactivity of a mononuclear Cu(II)-alkylperoxo complex
Aromatic hydroxylation reactivity of a mononuclear Cu(II)-alkylperoxo complex
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DOI：
10.1021/ja071623g
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发表时间：
2007-06-13
影响因子：
15
通讯作者：
Itoh, Shinobu
中科院分区：
文献类型：
--
作者：
Kunishita, Atsushi;Teraoka, Junji;Itoh, Shinobu
在三乙胺（NEt 3）存在下，在丙酮中，由在吡啶环（L-X）的6位上含有间取代苯基的三齿双（吡啶甲基）胺配体负载的铜（II）络合物1（X）与H2 O2反应，生成铜（II）-烷基过氧物种2（X）[2-羟基-2-氢过氧丙烷（HHPP）加合物]。烷基过氧中间体2（X）经历有效的芳族配体羟基化反应，经由另一中间体3（X）产生酚盐络合物4（X）。本文报道了芳烃羟基化反应的动力学研究和2（X）的光谱表征。
Reaction of copper(II) complex 1(X) supported by the tridentate bis(pyridylmethyl)amine ligand containing m-substituted phenyl groups at the 6-positions of the pyridine rings (L-X) with H2O2 in the presence of triethylamine (NEt3) in acetone generates a copper(II)-alkylperoxo species 2(X) [2-hydroxy-2-hydroperoxypropane (HHPP) adduct]. The alkylperoxo intermediate 2(X) undergoes an efficient aromatic ligand hydroxylation reaction, producing a phenolate complex 4(X) via another intermediate 3(X). Kinetic studies on the aromatic hydroxylation process are reported together with spectral characterization of 2(X).