Catalytic Reduction of Cyanide to Ammonia and Methane at a Mononuclear Fe Site

Johansen, Christian M.; Peters, Jonas C.

doi:10.1021/jacs.3c12395

Catalytic Reduction of Cyanide to Ammonia and Methane at a Mononuclear Fe Site

Journal Article · Fri Feb 16 00:00:00 EST 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c12395· OSTI ID:2471123

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California Institute of Technology, Pasadena, CA (United States)

Nitrogenase enzymes catalyze nitrogen reduction (N₂R) to ammonia and also the reduction of non-native substrates, including the 7H⁺/6e^– reduction of cyanide to CH₄ and NH₃. CN^– and N₂ are isoelectronic, and it is hence fascinating to compare the mechanisms of synthetic Fe catalysts capable of both CN^– and N₂ reduction. Here, we describe the catalytic reduction of CN^– to NH₃ and CH₄ by a highly selective (P₃^Si)Fe(CN) catalyst (P₃^Si represents a tris(phosphine)silyl ligand). Catalysis is driven in the presence of excess acid ([Ph₂NH₂]OTf) and reductant ((C₆H₆)₂Cr), with turnover as high as 73 demonstrated.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: NERSC; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2471123

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 8 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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