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Heterolytic H2 Activation Mediated by Low-Coordinate L3Fe-(μ-N)-FeL3 Complexes to Generate Fe(μ-NH)(μ-H)Fe Species

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journal contribution
posted on 28.09.2005, 00:00 by Steven D. Brown, Mark P. Mehn, Jonas C. Peters
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)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(μ-N)FeIIL3 and L3FeIII(μ-NH)(μ-H)FeIIL3, populate doublet ground states with thermally accessible higher spin states.