Synthesis and Characterization of a (μ‐η2:η2‐Peroxido)dicopper(II) Complex with N,N′,N″‐Triisopropyl‐cis,cis‐1,3,5‐triaminocyclohexane (R3TACH, R = iPr): Selective Preparation of (μ‐η2:η2‐Peroxido)dicopper(II) and Bis(μ‐oxido)dicopper(III) Species Regulated by Substituent Groups
Synthesis and Characterization of a (μ‐η2:η2‐Peroxido)dicopper(II) Complex with N,N′,N″‐Triisopropyl‐cis,cis‐1,3,5‐triaminocyclohexane (R3TACH, R = iPr): Selective Preparation of (μ‐η2:η2‐Peroxido)dicopper(II) and Bis(μ‐oxido)dicopper(III) Species Regulated by Substituent Groups
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(μ-η2:η2-过氧化)二铜(II)与N,N,N"-三异丙基-顺,顺-1,3,5-三氨基环己烷(R3TACH, R = iPr)配合物的合成和表征：选择性取代基调节的(μ-η2:η2-过氧化)二铜(II)和双(μ-氧化)二铜(III)物质的制备
DOI：
10.1002/ejic.201200228
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发表时间：
2012
影响因子：
2.3
通讯作者：
H. Masuda
中科院分区：
文献类型：
--
作者：
J. Matsumoto;Yuji Kajita;H. Masuda
N,N '，N″-三异丙基顺式，顺式-1,3,5-三氨基环己烷（iPr3TACH）的新CuI配合物，[Cu(iPr3TACH)(MeCN)](X)，在-80℃下立即与二氧反应生成（μ-η2:η2-过氧化物）二铜（II）配合物。这一观察结果与之前报道的其他TACH配体（Et3TACH、iBu3TACH和Bn3TACH）的铜(I)配合物在相同的反应条件下与二氧反应生成的双（μ-氧化）二铜（III）配合物有明显的不同。这种选择性制备已经被解释为围绕金属中心的TACH配体所提供的结构特异性。所制得的（μ-η2:η2-过氧化物）双铜（II）配合物表现出邻羟基化反应，以过氧化物中间体为基础，产率约为50%。双（μ-氧化）二铜（III）配合物与其他TACH衍生物不能与酚酸盐氧化。从酪氨酸酶反应机理的角度讨论了（μ-η2:η2-过氧化物）铜芯。
The new CuI complex of N,N′,N″-triisopropyl-cis,cis-1,3,5-triaminocyclohexane (iPr3TACH), [Cu(iPr3TACH)(MeCN)](X), immediately reacts with dioxygen at –80 °C to give a (μ-η2:η2-peroxido)dicopper(II) complex. This observation is significantly different from the previously reported cases of bis(μ-oxido)dicopper(III) complexes that were generated by the reaction of copper(I) complexes of other TACH ligands (Et3TACH, iBu3TACH, and Bn3TACH) with dioxygen under the same reaction conditions. Such selective preparations have been explained in terms of the structural specificity provided by the TACH ligands that surround the metal centers. The obtained (μ-η2:η2-peroxido)dicopper(II) complex exhibits ortho-hydroxylation of a phenolate to ortho-quinone with ca. 50 % yield based on the peroxido intermediate. The bis(μ-oxido)dicopper(III) complexes with other TACH derivatives are not capable of oxygenation of phenolate. The (μ-η2:η2-peroxido)dicopper core is discussed in the context of the reaction mechanism of tyrosinase.
影响因子：
5.6
作者：
Cuff, ME;Miller, KI;Hendrickson, WA
通讯作者：
Hendrickson, WA
影响因子：
4.6
作者：
Lanying Q. Hatcher;M. Vance;Amy A. Narducci Sarjeant;E. Solomon;K. Karlin
通讯作者：
Lanying Q. Hatcher;M. Vance;Amy A. Narducci Sarjeant;E. Solomon;K. Karlin
影响因子：
15
作者：
Op't Holt BT;Vance MA;Mirica LM;Heppner DE;Stack TD;Solomon EI
通讯作者：
Solomon EI