Department of Chemistry, University of Oregon, Eugene, Oregon 97403, USA.
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。
