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从空气中通过diarylimine铁复合体从空气中选择性提取N2

Erika R Bartholomew¹, Emily C Volpe, Peter T Wolczanski

¹Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, United States.

Journal of the American Chemical Society

|February 1, 2013

概括

这项研究合成了新的铁复合体与diarylimine连接体. 这些复合物选择性地将二 (N2) 与氧 (O2) 结合在一起,显示出固定应用的潜力.

科学领域:

有机金属化学有机金属化学
协调化学协调化学
材料科学材料科学材料科学

背景情况:

铁复合物在各种催化过程中至关重要.
了解连接体对金属中心活性的影响,是设计新催化剂的关键.
选择性气体结合是协调化学的一个重大挑战.

研究的目的:

为了合成和表征新型的铁复合物,其中包括正位置换的日利胺连接体.
研究这些复合物的对小气体分子,特别是N2和O2的反应性.
阐明了决定N2与O2的选择性结合的因素.

主要方法:

铁复合物的合成通过cis-(Me3P) 4FeMe2与正位置换的日利胺的反应.
使用光谱技术和X射线晶体学对产生的复合体进行表征.
气体结合研究涉及暴露于N2,O2,CO,NH3,H2和其他小分子.
计算计算以确定绑定事件的热力学和动力学有利性.

主要成果:

成功合成了{mer-κC,N,C'-(Ar-2-yl) CH2NCH(Ar'-2-yl)}Fe(PMe3) 3类型的新型铁复合体.
这些复合物在暴露于空气或N2时,可选择性地用N2取代素联体,形成{mer-κC,N,C'-(Ar-2-yl) CH2NCH(Ar'-2-yl) }FePMe3) 2L (L = N2).
二和氨的结合与N2相似,同时也形成了CO,CNMe和N2CPh2的添加物.
计算分析表明,二添加物 (2b) 在热力学和动力学上比潜在的Fe (III) 超氧化物复合物更受青.

结论:

合成的铁复合体对氧气上的二结合具有显著的选择性.
与O2相比,观察到的选择性归因于N2结合路径的系统间交叉点比O2更高.
这些发现为选择性固化的铁基催化剂的设计提供了洞察力.

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