An isolable, nonreducible high-valent manganese(V) imido corrolazine complex

被引：33
|
作者：
Lansky, David E. [1 ]
Kosack, Joseph R. [1 ]
Sarjeant, Amy A. Narducci [1 ]
Goldberg, David P. [1 ]
机构：
[1] Johns Hopkins Univ, Dept Chem, Baltimore, MD 21218 USA
来源：
INORGANIC CHEMISTRY | 2006年 / 45卷 / 21期
关键词：
D O I：
10.1021/ic0609251
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The manganese(V) imido complex [(TBP(8)Cz)Mn-V(NMes)] (2) was synthesized from the Mn-III complex [(TBP8Cz) MnIII] (1) and thermolysis of mesityl azide. An X-ray structure of 2 reveals a short Mn-N distance [1.595(4)angstrom], consistent with the Mn-N triple bond expected for a manganese(V) imido species. This high-valent species is remarkably inert to one- and two-electron reductive processes such as NR group transfer to alkenes or H-atom abstraction from O-H bonds. Electrochemical studies support this lack of reactivity. In contrast, oxidation of 2 is easily accomplished by treatment with [(4-BrC6H4)(3)N]center dot+SbCl6, giving a d-radical-cation complex.
引用
收藏
页码：8477 / 8479
页数：3
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