Proton-Coupled Reduction of an Iron Cyanide Complex to Methane and Ammonia
- Creators
- Rittle, Jonathan
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Peters, Jonas C.
Abstract
Nitrogenase enzymes mediate the six-electron reductive cleavage of cyanide to CH_4 and NH_3. Herein we demonstrate for the first time the liberation of CH_4 and NH_3 from a well-defined iron cyanide coordination complex, [SiP^(iPr)_3]Fe(CN) (where [SiP^(iPr)_3] represents a tris(phosphine)silyl ligand), on exposure to proton and electron equivalents. [SiP^(iPr)_3]Fe(CN) additionally serves as a useful entry point to rare examples of terminally-bound Fe(CNH) and Fe(CNH_2) species that, in accord with preliminary mechanistic studies, are plausible intermediates of the cyanide reductive protonation to generate CH_4 and NH_3. Comparative studies with a related [SiP^(iPr)_3]Fe(CNMe_2) complex suggests the possibility of multiple, competing mechanisms for cyanide activation and reduction.
Additional Information
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Received: June 30, 2016; First published: 8 September 2016. This work was supported by the NIH (grant number GM 070757) and the NSF (GRFP to J.R.). We thank Lawrence Henling and Michael Takase for assistance with XRD studies, and Kathryn Perez and Nathan Dalleska for assistance with GC experiments.Attached Files
Accepted Version - nihms-821345.pdf
Supplemental Material - anie201606366-sup-0001-misc_information.pdf
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Additional details
- PMCID
- PMC5065330
- Eprint ID
- 70271
- DOI
- 10.1002/anie.201606366
- Resolver ID
- CaltechAUTHORS:20160912-090559386
- GM 070757
- NIH
- NSF Graduate Research Fellowship
- Created
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2016-09-12Created from EPrint's datestamp field
- Updated
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2021-11-11Created from EPrint's last_modified field