Two-State Reactivity in Iron-Catalyzed Alkene Isomerization Confers σ-Base Resistance
Two-State Reactivity in Iron-Catalyzed Alkene Isomerization Confers σ-Base Resistance
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DOI：
10.1021/jacs.0c07300
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发表时间：
2020-09-09
影响因子：
15
通讯作者：
Smith, Jeremy M.
中科院分区：
文献类型：
--
作者：
Lutz, Sean A.;Hickey, Anne K.;Smith, Jeremy M.
低配位、高自旋（S = 3/2）的有机金属铁（I）配合物是烯烃异构化的催化剂。实验和计算机理的研究相结合，支持烯烃异构化的烯丙基机制发生的机制。重要的是，虽然底物结合发生在S = 3/2表面上，但氧化加成至η（1）-烯丙基中间体仅发生在S = 1/2表面上。由于这种自旋状态的变化是唯一可能的，当烯烃基板被绑定，催化剂具有高免疫力，典型的σ碱毒物由于反键相互作用的高自旋状态。
A low-coordinate, high spin (S = 3/2) organometallic iron(I) complex is a catalyst for the isomerization of alkenes. A combination of experimental and computational mechanistic studies supports a mechanism in which alkene isomerization occurs by the allyl mechanism. Importantly, while substrate binding occurs on the S = 3/2 surface, oxidative addition to an eta(1)-allyl intermediate only occurs on the S = 1/2 surface. Since this spin state change is only possible when the alkene substrate is bound, the catalyst has high immunity to typical sigma-base poisons due to the antibonding interactions of the high spin state.