Brown Steven D, Mehn Mark P, Peters Jonas C
Division of Chemistry and Chemical Engineering, Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125, USA.
J Am Chem Soc. 2005 Sep 28;127(38):13146-7. doi: 10.1021/ja0544509.
The diiron mu-nitride complexes, {L3FeII(mu-N)FeIIL3}- and L3FeIII(mu-N)FeIIL3, heterolytically activate hydrogen (1 atm) at ambient temperature in solution (L3 = [PhB(CH2PPh2)3]-). These transformations lead to structurally unique {L3FeII(mu-NH)(mu-H)FeIIL3}- and L3FeIII(mu-NH)(mu-H)FeIIL3 products. X-ray data establish a marked reduction in the Fe-Fe distance upon H2 uptake, and spectroscopic data establish both FeIIFeII species to be diamagnetic, whereas the FeIIIFeII species, L3FeIII(mu-N)FeIIL3 and L3FeIII(mu-NH)(mu-H)FeIIL3, populate doublet ground states with thermally accessible higher spin states.
二铁μ-氮配合物{L3FeII(μ-N)FeIIL3}-和L3FeIII(μ-N)FeIIL3在溶液中（L3 = [PhB(CH2PPh2)3]-）于室温下对氢气（1个大气压）进行异裂活化。这些转化产生了结构独特的{L3FeII(μ-NH)(μ-H)FeIIL3}-和L3FeIII(μ-NH)(μ-H)FeIIL3产物。X射线数据表明，吸收氢气后Fe-Fe距离显著缩短；光谱数据表明，两种FeIIFeII物种均为抗磁性，而FeIIIFeII物种L3FeIII(μ-N)FeIIL3和L3FeIII(μ-NH)(μ-H)FeIIL3具有热可及的较高自旋态的双重基态。
