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首页> 外文期刊>Proceedings of the National Academy of Sciences of the United States of America >Inner-sphere two-electron reduction leads to cleavage and functionalization of coordinated dinitrogen
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Inner-sphere two-electron reduction leads to cleavage and functionalization of coordinated dinitrogen

机译：内层双电子还原导致配位二氮的裂解和功能化

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Activation of molecular nitrogen by transition metal complexes is an area of current interest as investigations using the inert N-2 molecule to produce higher-value organonitrogen compounds intensify. In an attempt to extend the addition of hydride reagents E-H (where E = BR2, AIR(2), and SiR3) to the dinitrogen complex ([NPN]Ta)(2)(mu-H)(2)(mu-eta(2):eta(2)-N-2) [1; where NPN = (PhNSiMe2CH2)(2)PPh], the reaction with zirconocene chlorohydride, [Cp2Zr(Cl)H](x), was examined. The crystalline product formed in 35% yield was determined to be ([NP(N)N]Ta)(mu-H)(2)(mu-N)(Ta[NPN])(ZrCP2) (2) in which the coordinated N-2 has been cleaved to form a phosphinimide bridging between Ta and Zr and a triply bridging nitride. The mechanism of this reaction was examined to determine the fate of the chloride and hydricle ligands attached to Zr in the starting zirconocene reagent. Using the zirconocene dihydride dimer ([Cp2ZrH2](2)), a higher yield of 2 was obtained (76%), and H-2 was also observed by H-1 NMR spectroscopy. To probe the origin of the eliminated H-2, the dideuterated dinitrogen complex ([NPN]Ta)(2)(tLID)(2)(mu-eta(1):n(2)-N-2) (d(2)-1) was allowed to react with ([CP2ZrH2](2)), which resulted in the formation of ([NP(N)N]Ta)(mu-D)(2)(mu-N)(Ta[NPN]) (ZrCP2), (d(2)-2), with no evidence of hydrogen for deuterium scrambling between the starting zirconocene dihydride and the ditantalum dinitrogen complex. Studies into the use of preformed Zr(II) and Ti(II) reagents were also performed. The proposed mechanism involves initial adduct formation that facilitates inner-sphere electron transfer to cleave the N-N bond to form a species with bridging nitrides, one of which is transformed by nucleophilic attack of a phosphine donor to generate the observed phosphinimide.
机译：过渡金属配合物对分子氮的活化作用是当前研究的热点，这是利用惰性N-2分子生产更高价值的有机氮化合物的研究所引起的。为了扩展将氢化物试剂EH（其中E = BR2，AIR（2）和SiR3）添加到二氮配合物（[NPN] Ta）（2）（mu-H）（2）（mu-eta）中的尝试（2）：eta（2）-N-2）[1；其中NPN =（PhNSiMe2CH2）（2）PPh]，检查了与氧化锆茂锆[Cp2Zr（Cl）H]（x）的反应。确定以35％的收率形成的结晶产物为（[NP（N）N] Ta）（mu-H）（2）（mu-N）（Ta [NPN]）（ZrCP2）（2）配位的N-2被裂解形成在Ta和Zr之间桥接的次膦酰亚胺和三重桥接的氮化物。检查了该反应的机理，以确定起始锆茂试剂中与Zr连接的氯化物和水合配体的命运。使用二茂锆锆二聚体（[Cp2ZrH2]（2）），可获得更高的产率2（76％），并且还通过H-1 NMR光谱观察到H-2。为了探查消除的H-2的起源，使用双氘二氮配合物（[NPN] Ta）（2）（tLID）（2）（mu-eta（1）：n（2）-N-2）（d（ 2）-1）与（[CP2ZrH2]（2））反应，导致形成[[NP（N）N] Ta）（mu-D）（2）（mu-N）（Ta [NPN]）（ZrCP2），（d（2）-2），没有证据表明氢在起始的二茂锆或二钽二氮配合物之间发生氘争夺。还进行了有关使用预制Zr（II）和Ti（II）试剂的研究。拟议的机制涉及初始加合物的形成，该加合物的形成促进内球电子的传输，以裂解N-N键形成具有桥连氮化物的物种，其中一种通过膦供体的亲核攻击而转化，从而生成观察到的次膦酰亚胺。

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