The Direct Oxidative Addition of O2 to a Mononuclear Cr(I) Complex Is Spin Forbidden

被引：27
作者：
Dai, Fang [1 ]
Yap, Glenn P. A. [1 ]
Theopold, Klaus H. [1 ]
机构：
[1] Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 45期
关键词：
TRANSITION-METAL-COMPLEXES; DIOXYGEN ACTIVATION; WATER OXIDATION; REACTIVITY; OXYGEN; EPOXIDATION; GENERATION; CLEAVAGE; STATES; BONDS;
D O I：
10.1021/ja408357x
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Mononuclear chromium(I) alkyne complex (i-Pr2Ph)(2)nacnacCr(eta(2)-C-2(SiMe3)(2)) (1) reacts rapidly with dioxygen to yield chromium(V) dioxo species (i-Pr2Ph)(2)nacnacCr(O)(2) (2). The mechanism of this oxygen cleavage has been studied experimentally and computationally. Isotope labeling studies rule out a direct four-electron oxidative addition of O-2 to one chromium atom, which involves a spin-forbidden transformation. Instead, the reaction likely proceeds via an unsymmetric binuclear chromium bis(mu-oxo) complex. The latter has been independently prepared and structurally characterized. Its reactivity with O-2 is consistent with the proposed mechanism.
引用
收藏
页码：16774 / 16776
页数：3
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