DFT Investigation of H Activation by [M(NHPnPr)('S3')] (M = Ni, Pd). Insight into Key Factors Relevant to the Design of Hydrogenase Functional Models.
Density functional theory has been used to investigate the reaction between H and [Ni(NHPnPr)-(`S3')] or [Pd(NHPnPr)('S3')], where `S3' = bis(2-sulfanylphenyl)sulfide(2-), which are among the few synthetic complexes featuring a metal coordination environment similar to that observed in the [NiFe] hy...
| Publicado en: | Journal of the American Chemical Society Vol. 127; no. 38; pp. 13180 - 13190 |
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| Autores principales: | , , , |
| Formato: | Artículo |
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American Chemical Society
9/28/2005
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| 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=18502509&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 18502509 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: 9/28/2005 vid: 127 iid: 38 pid: 997 pub: American Chemical Society artinfo: ui: 18502509 10.1021/ja0508424 ppf: 13180 ppct: 10 formats: tig: atl: DFT Investigation of H Activation by [M(NHPnPr)('S3')] (M = Ni, Pd). Insight into Key Factors Relevant to the Design of Hydrogenase Functional Models. aug: au: Zampella, Giuseppe Bruschi, Maurizio Fantucci, Piercarlo De Gioia, Luca affil: Department of Biotechnology and Biosciences, University of Milan-Bicocca, Piazza della Scienza 2, I-20156 Milan, Italy. Department of Environmental Sciences, University of Milan-Bicocca, Piazza della Scienza 2, I-20156 Milan, Italy. su: Density functionals Functional analysis Chemical reactions Hydrogenase Metathesis reactions Catalysts sug: subj: Density functionals Functional analysis Chemical reactions Hydrogenase Metathesis reactions Catalysts ab: Density functional theory has been used to investigate the reaction between H and [Ni(NHPnPr)-(`S3')] or [Pd(NHPnPr)('S3')], where `S3' = bis(2-sulfanylphenyl)sulfide(2-), which are among the few synthetic complexes featuring a metal coordination environment similar to that observed in the [NiFe] hydrogenase active site and capable of catalyzing H heterolytic cleavage. Results allowed us to unravel the reaction mechanism, which is consistent with an oxidative addition—hydrogen migration pathway for [Ni(NHPnPr)('S3')], whereas metathesis is also possible with [Pd(NHPnPr)('S3')]. Unexpectedly, H binding and activation implies structural reorganization of the metal coordination environment. It turns out that the structural rearrangement in [Ni(NHPnPr)('S3')] and [Pd(NHPnPr)('S3')) can take place due to the peculiar structural features of the Ni and Pd ligands, explaining the remarkable catalytic properties. However, the structural reorganization is the most unfavorable step along the H cleavage pathway (ΔG > 100 kJ mol), an observation that is relevant for the design and synthesis of novel biomimetic catalysts. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2005 holdings: @attributes: islocal: N |
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