Yelle Robert B, Crossland Justin L, Szymczak Nathaniel K, Tyler David R
Computational Science Institute, 5294 University of Oregon, 1600 Millrace Drive Suite 105, Eugene, Oregon 97403, USA.
Inorg Chem. 2009 Feb 2;48(3):861-71. doi: 10.1021/ic800930t.
Electronic structure calculations using density functional theory were performed on potential intermediates in the reaction of Fe(dmpe)(2)N(2) (dmpe = 1,2-bis(dimethylphosphino)ethane) with protons. Three mechanisms were investigated and compared, and the possibility of a two-electron reduction by a sacrificial Fe(dmpe)(2)N(2) complex was considered in each mechanism. A Chatt-like mechanism, involving the stepwise addition of protons to the terminal nitrogen, was found to be the least favorable. A second pathway involving dimerization of the Fe(dmpe)(2)N(2) complex, followed by the stepwise addition of protons leading to hydrazine, was found to be energetically favorable; however many of the dimeric intermediates prefer to dissociate into monomers. A third mechanism proceeding through diazene and hydrazine intermediates, formed by alternating protonation of each nitrogen atom, was found to be the most energetically favorable.
利用密度泛函理论对Fe(dmpe)₂N₂（dmpe = 1,2 - 双（二甲基膦基）乙烷）与质子反应中的潜在中间体进行了电子结构计算。研究并比较了三种反应机理，每种机理都考虑了牺牲性Fe(dmpe)₂N₂配合物进行双电子还原的可能性。发现一种类似查特机理，即质子逐步加成到末端氮原子上，是最不利的。第二种途径涉及Fe(dmpe)₂N₂配合物的二聚化，然后质子逐步加成生成肼，在能量上是有利的；然而，许多二聚中间体更倾向于解离成单体。发现第三种机理通过二氮烯和肼中间体进行，由每个氮原子交替质子化形成，在能量上是最有利的。
