Heterolytic H2 activation mediated by low-coordinate L3Fe-(mu-N)-FeL3 complexes to generate Fe(mu-NH)(mu-H)Fe species |
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| Authors: | Brown Steven D Mehn Mark P Peters Jonas C |
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| Institution: | Division of Chemistry and Chemical Engineering, Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125, USA. |
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| Abstract: | 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. |
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