Heterolytic H2 activation mediated by low-coordinate L3Fe-(μ-N)-FeL3 complexes to generate Fe(μ-NH)(μ-H)Fe species
Heterolytic H2 activation mediated by low-coordinate L3Fe-(μ-N)-FeL3 complexes to generate Fe(μ-NH)(μ-H)Fe species
复制标题
DOI：
10.1021/ja0544509
复制
发表时间：
2005-09-28
影响因子：
15
通讯作者：
Peters, JC
中科院分区：
文献类型：
--
作者：
Brown, SD;Mehn, MP;Peters, JC
二铁μ-氮化物配合物{L3 FeII（μ-N）FeIIL 3}-和L3 FeIII（μ-N）FeIIL 3在环境温度下在溶液中异相活化氢（1 atm）（L3= [PhB（CH 2 PPh 2）3]-）。这些转变导致结构独特的{L3 FeII（μ-NH）（μ-H）FeIIL 3}-和L3 FeIII（μ-NH）（μ-H）FeIIL 3产物。X射线数据表明，在吸收H2后，Fe−Fe距离显著缩短，光谱数据表明两种FeIIFeII物种都是反磁性的，而FeIIIFeII物种，L3 FeIII（μ-N）FeIIL 3和L3 FeIII（μ-NH）（μ-H）FeIIL 3，则占据了具有热可及的更高自旋态的双重基态。
The diiron μ-nitride complexes, {L3FeII(μ-N)FeIIL3}-and L3FeIII(μ-N)FeIIL3, heterolytically activate hydrogen (1 atm) at ambient temperature in solution (L3= [PhB(CH2PPh2)3]-). These transformations lead to structurally unique {L3FeII(μ-NH)(μ-H)FeIIL3}-and L3FeIII(μ-NH)(μ-H)FeIIL3products. X-ray data establish a marked reduction in the Fe−Fe distance upon H2uptake, and spectroscopic data establish both FeIIFeIIspecies to be diamagnetic, whereas the FeIIIFeIIspecies, L3FeIII(μ-N)FeIIL3and L3FeIII(μ-NH)(μ-H)FeIIL3, populate doublet ground states with thermally accessible higher spin states.