协调一系列 N2 还原中间体（N2H2、N2H4 和 NH3）到铁膦骨架上。
Coordination of a complete series of N2 reduction intermediates (N2H2, N2H4, and NH3) to an iron phosphine scaffold.
机构信息
Department of Chemistry, University of Oregon, Eugene, Oregon 97403, USA.
出版信息
Inorg Chem. 2012 Jan 2;51(1):439-45. doi: 10.1021/ic201873a. Epub 2011 Oct 21.
The series of dinitrogen reduction intermediates (N(2)H(2), N(2)H(4), and NH(3)) coordinated to the Fe(DMeOPrPE)(2)H(+)(DMeOPrPE = 1,2-[bis(dimethoxypropyl)phosphino]ethane) scaffold has been synthesized or generated. The synthesis of trans-[Fe(DMeOPrPE)(2)(NH(3))H][BPh(4)] and generation of trans-[Fe(DMeOPrPE)(2)(N(2)H(4))H][BPh(4)] were achieved by substitu tion of the dinitrogen ligand on trans-[Fe(DMeOPrPE)(2)(N(2))H][BPh(4)]. The trans-Fe(DMeOPrPE)(2)(N(2)H(2))H complex and its deprotonated conjugate base, trans-Fe(DMeOPrPE)(2)(N(2)H)H, were observed by (31)P and (1)H NMR from decomposition of trans-Fe(DMeOPrPE)(2)(N(2)H(4))H in the presence of excess hydrazine. Attempts to chemically oxidize trans-Fe(DMeOPrPE)(2)(N(2)H(4))H to trans-[Fe(DMeOPrPE)(2)(N(2)H(2))H][BPh(4)] with a variety of oxidizing agents yielded only decomposition products consistent with the intermediate formation of trans-Fe(DMeOPrPE)(2)(N(2)H(2))H prior to decomposition.
已合成或生成了与 Fe(DMeOPrPE)(2)H(+)（DMeOPrPE=1,2-双（二甲基丙氧基膦基）乙烷）支架配位的一系列二氮还原中间体（N(2)H(2)、N(2)H(4)和 NH(3)）。通过取代反式-[Fe(DMeOPrPE)(2)(N(2))H][BPh(4)]上的二氮配体，实现了 trans-[Fe(DMeOPrPE)(2)(NH(3))H][BPh(4)]和 trans-[Fe(DMeOPrPE)(2)(N(2)H(4))H][BPh(4)]的合成。trans-Fe(DMeOPrPE)(2)(N(2)H(2))H络合物及其去质子共轭碱 trans-Fe(DMeOPrPE)(2)(N(2)H)H，通过（31）P 和（1）H NMR 从 trans-Fe(DMeOPrPE)(2)(N(2)H(4))H在过量联氨存在下分解时观察到。尝试用各种氧化剂将 trans-Fe(DMeOPrPE)(2)(N(2)H(4))H化学氧化为 trans-[Fe(DMeOPrPE)(2)(N(2)H(2))H][BPh(4)]，但只得到与 trans-Fe(DMeOPrPE)(2)(N(2)H(2))H分解前中间体形成一致的分解产物。
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