DC Field | Value | Language |
---|---|---|
dc.contributor.author | Kim, Sangmin | ko |
dc.contributor.author | Zhong, Hongyu | ko |
dc.contributor.author | PARK, YOONSU | ko |
dc.contributor.author | Loose, Florian | ko |
dc.contributor.author | Chirik, Paul J. | ko |
dc.date.accessioned | 2022-01-13T06:40:20Z | - |
dc.date.available | 2022-01-13T06:40:20Z | - |
dc.date.created | 2022-01-13 | - |
dc.date.created | 2022-01-13 | - |
dc.date.created | 2022-01-13 | - |
dc.date.issued | 2020-05 | - |
dc.identifier.citation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.142, no.20, pp.9518 - 9524 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://hdl.handle.net/10203/291782 | - |
dc.description.abstract | The catalytic hydrogenation of a metal nitride to produce free ammonia using a rhodium hydride catalyst that promotes H-2 activation and hydrogen-atom transfer is described. The phenylimine-substituted rhodium complex (eta(5)-C5Me5)Rh-((PhI)-Ph-Me)H ((PhI)-Ph-Me = N-methyl-l-phenylethan-1-imine) exhibited higher thermal stability compared to the previously reported (eta(5)-C5Me5)Rh(ppy)H (ppy = 2-phenylpyridine). DFT calculations established that the two rhodium complexes have comparable Rh-H bond dissociation free energies of 51.8 kcal mol(-1) for (eta(5) C5Me5)Rh((PhI)-Ph-Me)H and 51.1 kcal mol(-1) for (eta(5)-C5Me5)Rh(ppy)H. In the presence of 10 mol% of the phenylimine rhodium precatalyst and 4 atm of H-2 in THF, the manganese nitride ((tBu)Salen)Mn N underwent hydrogenation to liberate free ammonia with up to 6 total turnovers of NH3 or 18 turnovers of H-center dot transfer. The phenylpyridine analogue proved inactive for ammonia synthesis under identical conditions owing to competing deleterious hydride transfer chemistry. Subsequent studies showed that the use of a non-polar solvent such as benzene suppressed formation of the cationic rhodium product resulting from the hydride transfer and enabled catalytic ammonia synthesis by proton-coupled electron transfer. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Catalytic Hydrogenation of a Manganese(V) Nitride to Ammonia | - |
dc.type | Article | - |
dc.identifier.wosid | 000537415600049 | - |
dc.identifier.scopusid | 2-s2.0-85085693218 | - |
dc.type.rims | ART | - |
dc.citation.volume | 142 | - |
dc.citation.issue | 20 | - |
dc.citation.beginningpage | 9518 | - |
dc.citation.endingpage | 9524 | - |
dc.citation.publicationname | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.identifier.doi | 10.1021/jacs.0c03346 | - |
dc.contributor.localauthor | PARK, YOONSU | - |
dc.contributor.nonIdAuthor | Kim, Sangmin | - |
dc.contributor.nonIdAuthor | Zhong, Hongyu | - |
dc.contributor.nonIdAuthor | Loose, Florian | - |
dc.contributor.nonIdAuthor | Chirik, Paul J. | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | COUPLED ELECTRON-TRANSFER | - |
dc.subject.keywordPlus | NITROGEN-FIXATION | - |
dc.subject.keywordPlus | RHODIUM(I) COMPLEXES | - |
dc.subject.keywordPlus | BOND STRENGTHS | - |
dc.subject.keywordPlus | DINITROGEN | - |
dc.subject.keywordPlus | MOLYBDENUM | - |
dc.subject.keywordPlus | REDUCTION | - |
dc.subject.keywordPlus | N-2 | - |
dc.subject.keywordPlus | FUNCTIONALIZATION | - |
dc.subject.keywordPlus | CONVERSION | - |
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