Selective Catalytic Reduction of N2 to N2H4 by a Simple Fe Complex
Selective Catalytic Reduction of N2 to N2H4 by a Simple Fe Complex
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DOI：
10.1021/jacs.6b08802
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发表时间：
2016-10-19
影响因子：
15
通讯作者：
Ashley, Andrew E.
中科院分区：
文献类型：
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作者：
Hill, Peter J.;Doyle, Laurence R.;Ashley, Andrew E.
分子铁化合物催化固定N-2是一个快速发展的领域，但迄今为止，很少有配合物能影响这一转化，而且没有一个是选择性的N2H4生产。本文报道了简单的Fe(0)配合物Fe(Et2PCH2CH2PEt2)(2)(N-2)(1)是一种有效的催化剂，可以选择性地将N-2 （bbb25分子N-2固定）转化为N2H4，同时产生约1分子NH3。值得注意的是，所使用的还原剂（CoCp*(2)）和酸（Ph2NH2OTf）比以前在合成铁化合物的N-2转换演示中使用的常规化学H+和e（-）源弱得多。这些结果表明，N-2在分子铁配合物上直接催化转化为肼氧化态是可行的，这种体系形成NH3的机制可能是通过Fe - N2H4中间体进行的。
The catalytic fixation of N-2 by molecular Fe compounds is a rapidly developing field, yet thus far few complexes can effect this transformation, and none are selective for N2H4 production. Herein we report that the simple Fe(0) complex Fe(Et2PCH2CH2PEt2)(2)(N-2) (1) is an efficient catalyst for the selective conversion of N-2 (>25 molecules N-2 fixed) into N2H4, attendant with the production of ca. one molecule of NH3. Notably, the reductant (CoCp*(2)) and acid (Ph2NH2OTf) used are considerably weaker than conventional chemical H+ and e(-) sources used in previous demonstrations of N-2 turnover by synthetic Fe compounds. These results show that the direct catalytic conversion of N-2 to the hydrazine oxidation state on molecular Fe complexes is viable and that the mechanism of NH3 formation by such systems may proceed via Fe N2H4 intermediates.