Hydrogenolysis of [PhBP3]FeN-p-tolyl:: Probing the reactivity of an iron imide with H2
Hydrogenolysis of [PhBP3]FeN-p-tolyl:: Probing the reactivity of an iron imide with H2
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DOI：
10.1021/ja0399122
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发表时间：
2004-04-14
影响因子：
15
通讯作者：
Peters, JC
中科院分区：
文献类型：
--
作者：
Brown, SD;Peters, JC
本文描述了低自旋（S= 1/2）铁（III）亚胺的还原氢解。在苯溶液中，用氢气还原[PhBP_3] Fe_（III）-N-对甲苯基。这种减少似乎是逐步进行的。观察到中间体S = 2铁（II）苯胺，[PhBP 3]Fe（N（H）-对甲苯基），并已独立产生和结构表征。在苯中长时间的氢解导致Fe−N键完全氢解，释放出H2 N-p-tolyl。由该步骤形成的主要含铁产物是抗磁性环己二烯基络合物[PhBP 3]Fe（η5-环己二烯基），其也已独立地制备和结构表征。有证据表明，最终的[PhBP 3]Fe（η5-环己二烯基）产物是通过苯插入到反应性[PhBP 3]FeII-H中间体中形成的。
This paper describes the reductive hydrogenolysis of a low-spin (S= 1/2) iron(III) imide. Pseudotetrahedral [PhBP3]FeIII⋮N-p-tolyl is reduced by hydrogen at ambient temperature and pressure in benzene solution. The reduction appears to proceed in a stepwise fashion. An intermediateS= 2 iron(II) anilide, [PhBP3]Fe(N(H)-p-tolyl), is observed and has been independently generated and structurally characterized. Prolonged hydrogenolysis in benzene results in the complete hydrogenolysis of the Fe−N linkage to release H2N-p-tolyl. The major iron-containing product formed from this step is the diamagnetic cyclohexadienyl complex, [PhBP3]Fe(η5-cyclohexadienyl), which has also been independently prepared and structurally characterized. Evidence is presented to suggest that the final [PhBP3]Fe(η5-cyclohexadienyl) product is formed via benzene insertion into a reactive [PhBP3]FeII-H intermediate.