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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Mechanisms for the Formation of NH3, N2H4, and N2H2 in the Protonation Reaction of Fe(DMeOPrPE)(2)N-2 {DMeOPrPE=1,2-bis[bis(methoxypropyl)phosphino]ethane}
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Mechanisms for the Formation of NH3, N2H4, and N2H2 in the Protonation Reaction of Fe(DMeOPrPE)(2)N-2 {DMeOPrPE=1,2-bis[bis(methoxypropyl)phosphino]ethane}

机译：Fe（DMeOPrPE）（2）N-2 {DMeOPrPE = 1,2-双[双（双（甲氧基丙基）膦基]乙烷}的质子化反应中NH3，N2H4和N2H2形成的机理

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Research from the author's laboratory is reviewed on the reaction of Fe(DMeOPrPE)(2)N-2 with acid to form ammonia and hydrazine {DMeOPrPE is the water-soluble, bidentate phosphine 1,2-bis[bis(methoxypropyl) phosphino]ethane}. DFT calculations suggested that a symmetric protonation mechanism was more favorable than either an asymmetric protonation mechanism or a dinuclear mechanism. Two symmetric protonation pathways were investigated by synthesizing or generating reaction intermediates. Among the various species synthesized or spectroscopically observed were hydrazine complexes, diazene complexes, and their deprotonated conjugate bases. A relatively long-lived intermediate in the protonation reaction, identified as [((DMeOPrPE)(2)Fe)(2)(mu-N-2)](2+), hints that a dinuclear path-way might be operating, but further mechanistic investigations suggested this species is likely forming in a side-reaction and is not involved in the formation of ammonia. The only source of electrons for the reduction of N-2 in the reaction is the Fe(DMeOPrPE)(2)N-2 complex. As discussed in this review, this feature will ultimately limit the yields of ammonia and hydrazine that can form in the reaction. The reactions pathways uncovered by this research are symmetric protonation pathways, and as such they are different from the "asymmetric" protonation pathway proposed for some Mo-N-2 complexes that protonate to form ammonia. Recent studies suggest a symmetric protonation pathway for nitrogenase (which has Fe in its active site), and it may well be a general conclusion that Fe-N-2 species produce ammonia via the symmetric protonation mechanism.
机译：作者实验室的研究综述了Fe（DMeOPrPE）（2）N-2与酸反应生成氨和肼的反应（DMeOPrPE是水溶性的二齿膦1,2-双[双（甲氧基丙基）膦基]乙烷}。 DFT计算表明，对称质子化机制比非对称质子化机制或双核机制都更有利。通过合成或生成反应中间体研究了两个对称的质子化途径。在合成或光谱观察到的各种物种中，有肼配合物，重氮配合物及其去质子化的共轭碱。质子化反应中相对较长寿的中间体，标识为[（（DMeOPrPE）（2）Fe）（2）（mu-N-2）]（2+），暗示双核途径可能正在起作用，但是进一步的机械研究表明，该物种很可能在副反应中形成，并且不参与氨的形成。 Fe（DMeOPrPE）（2）N-2络合物是反应中还原N-2的唯一电子源。如本评论所述，此功能最终将限制反应中可能形成的氨和肼的收率。这项研究发现的反应途径是对称的质子化途径，因此它们不同于为某些质子化生成氨的Mo-N-2络合物提出的“不对称”质子化途径。最近的研究表明，固氮酶的对称质子化途径（在其活性位点具有Fe），很可能是一个普遍的结论，即Fe-N-2物种通过对称质子化机理产生氨。

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