Snapshots of dioxygen activation by copper:: The structure of a 1:1 Cu/O2 adduct and its use in syntheses of asymmetric bis(μ-oxo) complexes
Snapshots of dioxygen activation by copper:: The structure of a 1:1 Cu/O2 adduct and its use in syntheses of asymmetric bis(μ-oxo) complexes
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DOI：
10.1021/ja027164v
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发表时间：
2002-09-11
影响因子：
15
通讯作者：
Tolman, WB
中科院分区：
文献类型：
--
作者：
Aboelella, NW;Lewis, EA;Tolman, WB
1:1 Cu/ o2加合物的x射线结构显示侧侧（η2） o2配位。密度泛函计算证实了结构，表明了Cu(III)−(O22-)共振形式的重要贡献，并提供了关键键相互作用的见解。由一种略有不同的β-二氯胺酸配体支撑的1:1加合物与Cu(I)试剂反应，形成了新的不对称双μ-氧(o)配合物，通过EPR、UV - vis、拉曼光谱以及x射线结构对其进行了鉴定。
The X-ray structure of a 1:1 Cu/O2adduct revealed side-on (η2) O2coordination. Density functional calculations corroborated the structure, indicated a significant contribution of a Cu(III)−(O22-) resonance form, and provided insights into the key bonding interactions. Reaction of a 1:1 adduct supported by a slightly different β-diketiminate ligand with Cu(I) reagents resulted in the formation of novel asymmetric bis(μ-oxo) complexes that were identified by EPR, UV−vis, and Raman spectroscopy, as well as by an X-ray structure in one instance.