Reversible O-O bond cleavage in copper-dioxygen isomers: impact of anion basicity.
Reversible O-O bond cleavage in copper-dioxygen isomers: impact of anion basicity.
复制标题
铜-双氧异构体中可逆的O-O键断裂：阴离子碱度的影响。
DOI：
10.1021/ja061132g
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发表时间：
2006
影响因子：
15
通讯作者：
Stack,TDanielP
中科院分区：
文献类型：
--
作者：
Ottenwaelder,Xavier;Rudd,DeanneJackson;Corbett,MaryC;Hodgson,KeithO;Hedman,Britt;Stack,TDanielP
N，N，N‘，N’-四乙基丙烷-1，3-二胺的铜(I)络合物低温氧化生成同时含有μ-η_2：η_2-过氧二铜(II)(P)和双(μ-氧代)二铜(III)(O)价异构体的溶液。P/O平衡位置取决于反阴离子的性质；碱性阴离子越多，P越有利。滴定和EXAFS实验以及密度泛函理论计算表明，磺酸盐阴离子向铜中心的轴向施主给电子/静电偏向于同分异构体。
Low-temperature oxygenation of copper(I) complexes ofN,N,N‘,N‘-tetraethylpropane-1,3-diamine yields solutions containing both μ-η2:η2-peroxodicopper(II) (P) and bis(μ-oxo)dicopper(III) (O) valence isomers. TheP/Oequilibrium position depends on the nature of the counteranion;Pis favored with more basic anions. Titration and EXAFS experiments as well as DFT calculations suggest that axial donation from a sulfonate anion to the copper centers imparts an electronic/electrostatic bias toward thePisomer.