Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 55, Issue 40, Pages 12262-12265Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201606366
Keywords
carbyne ligands; cyanide cleavage; iron complexes; nitrogenase; nitrogen fixation
Categories
Funding
- NIH [GM 070757]
- NSF (GRFP)
Ask authors/readers for more resources
Nitrogenase enzymes mediate the six-electron reductive cleavage of cyanide to CH4 and NH3. Herein we demonstrate for the first time the liberation of CH4 and NH3 from a well-defined iron cyanide coordination complex, [SiP3iPr]Fe(CN) (where [SiP3iPr] represents a tris(phosphine)silyl ligand), on exposure to proton and electron equivalents. [SiP3iPr]Fe(CN) additionally serves as a useful entry point to rare examples of terminally-bound Fe(CNH) and Fe(CNH2) species that, in accord with preliminary mechanistic studies, are plausible intermediates of the cyanide reductive protonation to generate CH4 and NH3. Comparative studies with a related [SiP3iPr]Fe(CNMe2) complex suggests the possibility of multiple, competing mechanisms for cyanide activation and reduction.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available