Thermodynamic Hydricities of Biomimetic Organic Hydride Donors.
Thermodynamic hydricities (ΔG) in acetonitrile and dimethyl sulfoxide have been calculated and experimentally measured for several metal-free hydride donors: NADH analogs (BNAH, CN-BNAH, Me-MNAH, HEH), methylene tetrahydromethanopterin analogs (BIMH, CAFH), acridine derivatives (Ph-AcrH, Me[sub 2]N-...
| Publicado en: | Journal of the American Chemical Society Vol. 140; no. 13; pp. 4569 - 4580 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
4/4/2018
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=128955146&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 128955146 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 4/4/2018 vid: 140 iid: 13 pid: 997 pub: American Chemical Society artinfo: ui: 128955146 10.1021/jacs.7b13526 ppf: 4569 ppct: 11 formats: tig: atl: Thermodynamic Hydricities of Biomimetic Organic Hydride Donors. aug: au: Ilic, Stefan Kadel, Usha Pandey Basdogan, Yasemin Keith, John A. Glusac, Ksenija D. affil: Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States Department of Chemistry, Center for Photochemical Sciences, Bowling Green State University, Bowling Green, Ohio 43403, United States Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States su: Transition metal hydrides Dimethyl sulfoxide Acridine derivatives Density functional theory Hydride transfer reactions Acetonitrile sug: subj: Transition metal hydrides Dimethyl sulfoxide Acridine derivatives Density functional theory Hydride transfer reactions Acetonitrile ab: Thermodynamic hydricities (ΔG) in acetonitrile and dimethyl sulfoxide have been calculated and experimentally measured for several metal-free hydride donors: NADH analogs (BNAH, CN-BNAH, Me-MNAH, HEH), methylene tetrahydromethanopterin analogs (BIMH, CAFH), acridine derivatives (Ph-AcrH, Me[sub 2]N-AcrH, T-AcrH, 4OH, 2OH, 3NH), and a triarylmethane derivative (6OH). The calculated hydricity values, obtained using density functional theory, showed a reasonably good match (within 3 kcal/ mol) with the experimental values, obtained using "potential pK" and "hydride-transfer" methods. The hydride donor abilities of model compounds were in the 48.7-85.8 kcal/mol (acetonitrile) and 46.9-84.1 kcal/mol (DMSO) range, making them comparable to previously studied first-row transition metal hydride complexes. To evaluate the relevance of entropic contribution to the overall hydricity, Gibbs free energy differences (ΔG) obtained in this work were compared with the enthalpy (ΔH) values obtained by others. The results indicate that, even though ΔH values exhibit the same trends as ΔG, the differences between room-temperature ΔG and ΔH values range from 3 to 9 kcal/mol. This study also reports a new metal-free hydride donor, namely, an acridine-based compound 3NH, whose hydricity exceeds that of NaBH. Collectively, this work gives a perspective of use metal-free hydride catalysts in fuel-forming and other reduction processes. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2018 holdings: @attributes: islocal: N |
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