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J Am Chem Soc. 2005 Sep 28;127(38):13146-7.

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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1
Division of Chemistry and Chemical Engineering, Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125, USA.

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.

PMID:
16173733
DOI:
10.1021/ja0544509
[Indexed for MEDLINE]
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