Heterolytic H2 activation mediated by low-coordinate L3Fe-(mu-N)-FeL3 complexes to generate Fe(mu-NH)(mu-H)Fe species.
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.
Brown
Steven D
SD
Division of Chemistry and Chemical Engineering, Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125, USA.
Mehn
Mark P
MP
Peters
Jonas C
JC
D018360:Crystallography, X-Ray; D006859:Hydrogen / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009584:Nitrogen / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
D008024:Ligands; D009942:Organometallic Compounds; D006859:Hydrogen; D007501:Iron; D009584:Nitrogen