钼-氨配合物中三个氢原子的抽提促进氨氧化。
Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo-NH Complex.
机构信息
Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory , P.O. Box 999, Richland, Washington 99352, United States.
Department of Chemistry, Washington State University , Pullman, Washington 99164, United States.
出版信息
J Am Chem Soc. 2017 Mar 1;139(8):2916-2919. doi: 10.1021/jacs.7b00002. Epub 2017 Feb 15.
We report ammonia oxidation by homolytic cleavage of all three H atoms from a [Mo-NH] 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≡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-NH] and formation of [Mo═NR].
我们报告了使用 2,4,6-三特丁基苯氧自由基使 [Mo-NH] 配合物中的所有三个 H 原子均发生均裂，从而实现氨氧化，生成 Mo-烷基亚氨基 ([Mo═NR]) 配合物（R = 2,4,6-三特丁基环己-2,5-二烯-1-酮）。[Mo═NR] 的化学还原在 N-C 键断裂时生成末端 Mo≡N 氮化物配合物，并且通过氮化物的质子化形成 [Mo═NH] 配合物。计算分析描述了从 [Mo-NH] 逐步去除三个 H 原子并形成 [Mo═NR] 的能量分布。
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