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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 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 dinitrogen at a bimetallic sulfur centre

机译：在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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The reduction of diazene complexes [Mo2Cp2(mu-SMe)(3)(mu-eta(2)-H-N=N-R)](+) (R=Ph (3a); Me (3b)) and of the hydrazido(2-) derivative [Mo2Cp2(mu-SMe)(3){mu-eta(1)-N=N(Me)H}](+) (1b) has been studied by cyclic voltammetry, controlled-potential electrolysis, and coulometry in THE The electrochemical reduction of 3 a in the presence of acid leads to cleavage of the N=N bond and produces aniline and either the amido complex [Mo2Cp2(mu-SMe)(3)- (mu-NH2)] 4 or the ammine complex [Mo2Cp2(mu-SMe)(3)(NH3)(X)] 5, depending on the initial concentration of acid (HX = HTsO or CF3CO2H). The N=N bond of the methyldiazene analogue 3b 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. ne 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 [Mo2Cp2(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 pathway for the reduction of N-2 at a dinuclear site of FeMoco is proposed on the basis of these results. [References: 93]
机译：重氮化合物[Mo2Cp2（mu-SMe）（3）（mu-eta（2）-HN = NR）]（+）（R = Ph（3a）; Me（3b））和肼基化合物的还原[2 -）衍生物[Mo2Cp2（mu-SMe）（3）{mu-eta（1）-N = N（Me）H}]（+）（1b）已通过循环伏安法，电势控制和库仑法研究在酸的存在下3a的电化学还原导致N = N键的裂解并产生苯胺和酰胺络合物[Mo2Cp2（mu-SMe）（3）-（mu-NH2）] 4或胺络合物[Mo2Cp2（mu-SMe）（3）（NH3）（X）] 5，具体取决于酸的初始浓度（HX = HTsO或CF3CO2H）。在相同条件下，甲基二氮杂类似物3b的N ＝ N键不断裂。 3a而不是3b经历N ＝ N键的还原裂解的能力归因于R基团对Mo-N（R）键的强度的电子控制。在HX存在下，甲基肼基（2-）化合物1b的电化学还原也导致N = N键断裂，形成甲胺，4（或5）和甲基二氮杂叠氮化合物[Mo2Cp2（mu-SMe）（ 3）（mu-eta（1）-N = N-Me）]。这些复合物的最后一个的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的途径。 [参考：93]

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