An Unusual Ligand Oxidation by a (μ-η2:η2-Peroxo)dicopper Compound: 1° > 3° C−H Bond Selectivity and a Novel Bis(μ-alkylperoxo)dicopper Intermediate
An Unusual Ligand Oxidation by a (μ-η2:η2-Peroxo)dicopper Compound: 1° > 3° C−H Bond Selectivity and a Novel Bis(μ-alkylperoxo)dicopper Intermediate
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(μ-η2:η2-过氧)二铜化合物的异常配体氧化：1° > 3° C−H 键选择性和新型双(μ-烷基过氧)二铜中间体
DOI：
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发表时间：
1998
期刊：
影响因子：
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通讯作者：
W. Tolman
中科院分区：
文献类型：
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作者：
J. Halfen;V. Young;W. Tolman
在用 O2 吹扫期间，在 -78 °C 下用 2,4-二叔丁基苯酚处理 [(LCu)2(μ-η2:η2-O2) (L = 1,4,7-三异丙基-1,4,7-三氮杂环壬烷) 时，在甲基而不是配体异丙基取代基通常更具反应性的次甲基位置发生氧化。这种意想不到的区域选择性的证实是从所示的双(μ-烷氧基)二铜(II)化合物的X射线结构中得到的，该化合物衍生自初始反应产物，一种独特的双(μ-烷基过氧)二铜(II)物质。
Oxygenation at the methyl instead of the usually more reactive methine position of a ligand isopropyl substituent occurred upon treatment of [(LCu)2(μ-η2:η2-O2) (L = 1,4,7-triisopropyl-1,4,7-triazacyclononane) with 2,4-di-tert-butylphenol at −78 °C during purging with O2. Confirmation of this unexpected regioselectivity was obtained from the X-ray structure of the shown bis(μ-alkoxo)dicopper(II) compound, which was derived from the initial reaction product, a unique bis(μ-alkylperoxo)dicopper(II) species.