Nitrogen Fixation Revisited on Iron(0) Dinitrogen Phosphine Complexes
Nitrogen Fixation Revisited on Iron(0) Dinitrogen Phosphine Complexes
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DOI：
10.1021/acs.inorgchem.5b00211
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发表时间：
2015-05-18
影响因子：
4.6
通讯作者：
Li, Hsiu L.
中科院分区：
文献类型：
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作者：
Field, Leslie D.;Hazari, Nilay;Li, Hsiu L.
对用酸处理 [Fe(N-2)(PP)(2)]（PP = depe, dmpe）的重新研究表明没有形成铵。相反，观察到金属中心快速质子化以产生氢化物络合物。用甲基化剂如三氟甲磺酸甲酯或甲苯磺酸甲酯处理[Fe(N-2)(dmpe)(2)]导致金属中心甲基化，得到[FeMe(N-2)(dmpe)(2)](+)。然而，用三甲基甲硅烷基三氟甲磺酸酯处理[Fe(N-2)(dmpe)(2)]导致在随后用酸处理时在二氮下反应，提供NH4+。通过 N-15 NMR 光谱将侧键联肼络合物 [Fe-(N2H4)(dmpe)(2)](2+) 和双（氨）络合物 [Fe(NH3)(2)(dmpe)(2)](2+) 鉴定为反应混合物中形成的其他物质。
A reinvestigation of the treatment of [Fe(N-2)(PP)(2)] (PP = depe, dmpe) with acid revealed no ammonium formation. Instead, rapid protonation at the metal center to give hydride Complexes was observed. Treatment of [Fe(N-2)(dmpe)(2)] with methylating agents such as methyl triflate or methyl tosylate resulted methylation of the metal center to afford [FeMe(N-2)(dmpe)(2)](+). Treatment of [Fe(N-2)(dmpe)(2)] With trimethylsilyl triflate, however, resulted in reactibn at dinitrogen affording NH4+ on subsequent treatment with acid. The side-on bound hydrazine complex [Fe-(N2H4)(dmpe)(2)](2+) and bis(ammonia) complex [Fe(NH3)(2)(dmpe)(2)](2+) were identified by N-15 NMR spectroscopy as other species formed in the reaction mixture.