Field Leslie D, Hazari Nilay, Li Hsiu L
†School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia.
‡Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520, United States.
Inorg Chem. 2015 May 18;54(10):4768-76. doi: 10.1021/acs.inorgchem.5b00211. Epub 2015 May 6.
A reinvestigation of the treatment of [Fe(N2)(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(N2)(dmpe)2] with methylating agents such as methyl triflate or methyl tosylate resulted in methylation of the metal center to afford FeMe(N2)(dmpe)2. Treatment of [Fe(N2)(dmpe)2] with trimethylsilyl triflate, however, resulted in reaction at dinitrogen affording NH4(+) on subsequent treatment with acid. The side-on bound hydrazine complex Fe(N2H4)(dmpe)2 and bis(ammonia) complex Fe(NH3)2(dmpe)2 were identified by (15)N NMR spectroscopy as other species formed in the reaction mixture.
对[Fe(N₂)(PP)₂]（PP = depe、dmpe）进行酸处理的重新研究表明没有铵生成。相反，观察到金属中心快速质子化生成氢化物配合物。用甲基化试剂如三氟甲磺酸甲酯或对甲苯磺酸甲酯处理[Fe(N₂)(dmpe)₂]导致金属中心甲基化，得到FeMe(N₂)(dmpe)₂。然而，用三氟甲磺酸三甲基硅酯处理[Fe(N₂)(dmpe)₂]，则导致在二氮处发生反应，随后用酸处理时生成NH₄(⁺)。通过¹⁵N核磁共振光谱鉴定出反应混合物中形成的其他物种为侧基配位的肼配合物Fe(N₂H₄)(dmpe)₂和双（氨）配合物Fe(NH₃)₂(dmpe)₂。
