Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo-NH3 Complex
Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo-NH3 Complex
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DOI：
10.1021/jacs.7b00002
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发表时间：
2017-03-01
影响因子：
15
通讯作者：
Mock, Michael T.
中科院分区：
文献类型：
--
作者：
Bhattacharya, Papri;Heiden, Zachariah M.;Mock, Michael T.
本文报道了用2，4，6-三叔丁基苯氧基将[Mo-NH_3]（+）络合物中的三个氢原子均裂，得到Mo-烷基亚氨基（[Mo=NR]（+））络合物（R = 2，4，6-三叔丁基环己-2，5-二烯-1-酮）。[Mo=NR]（+）的化学还原在N-C键断裂时产生与N氮化物络合物相当的末端Mo，并且[Mo=NH]（+）络合物通过氮化物的质子化形成。计算分析描述了从[Mo-NH 3]（+）中逐步去除三个H原子并形成[Mo=NR]（+）的能量分布。
We report ammonia oxidation by homolytic cleavage of all three H atoms from a [Mo-NH3](+) complex using the 2,4,6-tri-tert-butylphenoxyl radical to yield a Mo-alkylimido ([Mo=NR](+)) complex (R = 2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one). Chemical reduction of [Mo=NR](+) generates a terminal Mo equivalent to N nitride complex upon N-C bond cleavage, and a [Mo=NH](+) complex is formed by protonation of the nitride. Computational analysis describes the energetic profile for the stepwise removal of three H atoms from [Mo-NH3](+) and formation of [Mo=NR](+).