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首页> 外文期刊>Chemistry: A European journal >Electrochemical Cleavage of N = N Bonds at a Mo_2(mu-SMe)_3 Site Relevant to the Biological Reduction of of Dinitrogen at a Bimetallic Sulfur Centre
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Electrochemical Cleavage of N = N Bonds at a Mo_2(mu-SMe)_3 Site Relevant to the Biological Reduction of of Dinitrogen at a Bimetallic Sulfur Centre

机译：Mo_2（mu-SMe）_3位点上的N = N键的电化学裂解与双金属硫中心的二氮的生物还原有关

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摘要

The reduction of diazene complexes [Mo_2Cp_2(mu-SMe)_3(mu-eta~2-H-N=N-R)]~+ (R = Ph (3a); Me(3b)) and of the hydrazido (2-) derivative [Mo_2Cp_2(mu-SMe)_3{mu-eta~1-N=N(Me)H}]~+ (1b) has been studied by cyclic voltammetry, controlled-potential electrolysis, and coulometry in THF. The electrochemical reduction of 3a in the presence of acid leads to cleavage of the N = N bond and produces aniline and either the amido complex [Mo_2Cp_2(mu-SMe)_(3~-) (mu-NH_2)] 4 or the ammine complex [Mo_2Cp_2(mu-SMe)_3(NH_3)(X)]5, depending on the initial concentration of acid (HX = HTsO or CF_3CO_2H). The N = N bond of the methyldiazene analogue 3nb is not cleaved under the same conditions. The ability of 3a but not 3b to undergo reductive cleavage of the N = N bond is attributed to electronic control of the strength of the Mo-N(R) bond by the R group. The electrochemical reduction of the methylhydrazido (2-) compound 1b in the presence of HX also results in cleavage of the N = N bond, with formation of methylamine, 4 (or 5) and the methyldiazenido complex [Mo_2Cp_2(mu-SMe)_3(mu-eta~1-N = N-Me)]. Formation of the last of these complexes indicates that two mechanisms (N = N bond cleavage and possibly H_2 production) are operative. A patheay for the reduction of N_2 at a dinuclear site of FeMoco is proposed on the basis of these results.
机译：重氮化合物[Mo_2Cp_2（mu-SMe）_3（mu-eta〜2-HN = NR）]〜+（R = Ph（3a）; Me（3b））和肼基衍生物（2-）的还原[ Mo_2Cp_2（mu-SMe）_3 {mu-eta〜1-N = N（Me）H}] ++（1b）已通过循环伏安法，控制电位电解和库仑法在THF中进行了研究。在酸的存在下3a的电化学还原导致N = N键的断裂并产生苯胺和酰胺络合物[Mo_2Cp_2（mu-SMe）_（3〜-）（mu-NH_2）] 4或胺络合物[Mo_2Cp_2（mu-SMe）_3（NH_3）（X）] 5，取决于酸的初始浓度（HX = HTsO或CF_3CO_2H）。在相同条件下，甲基二氮杂类似物3nb的N ＝ N键不断裂。 3a但不是3b经历N = N键还原裂解的能力归因于R基团对Mo-N（R）键强度的电子控制。在存在HX的条件下，对甲基肼基（2-）化合物1b进行电化学还原，还会导致N = N键断裂，形成甲胺4（或5）和甲基二氮杂叠氮化合物[Mo_2Cp_2（mu-SMe）_3 （mu-eta〜1-N = N-Me）]。这些复合物的最后形成表明有两种机制（N = N键断裂和可能的H_2产生）起作用。基于这些结果，提出了在FeMoco的双核位点还原N_2的方法。

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