Highly regioselective hydride transfer, oxidative dehydrogenation, and hydrogen-atom abstraction in the thermal gas-phase chemistry of [Zn(OH)](+)/C3H8
| dc.contributor.author | Wu, Xiao-Nan | |
| dc.contributor.author | Zhao, Hai-Tao | |
| dc.contributor.author | Li, Jilai | |
| dc.contributor.author | Schlangen, Maria | |
| dc.contributor.author | Schwarz, Helmut | |
| dc.date.accessioned | 2016-06-21T08:29:19Z | |
| dc.date.available | 2016-06-21T08:29:19Z | |
| dc.date.issued | 2014 | |
| dc.description.abstract | The thermal reactions of [Zn(OH)]+ with C3H8 have been studied by means of gas-phase experiments and computational investigation. Two types of C–H bond activation are observed in the experiment, and pertinent mechanistic features include inter alia: (i) the metal center of [Zn(OH)]+ serves as active site in the hydride transfer to generate [i-C3H7]+ as major product, (ii) generally, a high regioselectivity is accompanied by remarkable chemoselectivity: for example, the activation of a methyl C–H bond results mainly in the formation of water and [Zn(C3,H7)]+. According to computational work, this ionic product corresponds to [HZn(CH3CH[double bond, length as m-dash]CH2)]+. Attack of the zinc center at a secondary C–H bond leads preferentially to hydride transfer, thus giving rise to the generation of [i-C3H7]+; (iii) upon oxidative dehydrogenation (ODH), liberation of CH3CH2[double bond, length as m-dash]CH2 occurs to produce [HZn(H2O)]+. Both, ODH as well as H2O loss proceed through the same intermediate which is characterized by the fact that a methylene hydrogen atom from the substrate is transferred to the zinc and one hydrogen atom from the methyl group to the OH group of [Zn(OH)]+. The combined experimental/computational gas-phase study of C–H bond activation by zinc hydroxide provides mechanistic insight into related zinc-catalyzed large-scale processes and identifies the crucial role that the Lewis-acid character of zinc plays. | en |
| dc.description.sponsorship | DFG, EXC 314, Unifying Concepts in Catalysis | en |
| dc.identifier.eissn | 1463-9084 | |
| dc.identifier.issn | 1463-9076 | |
| dc.identifier.pmid | 25230924 | |
| dc.identifier.uri | https://depositonce.tu-berlin.de/handle/11303/5571 | |
| dc.identifier.uri | http://dx.doi.org/10.14279/depositonce-5200 | |
| dc.language.iso | en | |
| dc.rights.uri | https://creativecommons.org/licenses/by/3.0/ | |
| dc.subject.ddc | 540 Chemie und zugeordnete Wissenschaften | de |
| dc.title | Highly regioselective hydride transfer, oxidative dehydrogenation, and hydrogen-atom abstraction in the thermal gas-phase chemistry of [Zn(OH)](+)/C3H8 | en |
| dc.type | Article | en |
| dc.type.version | publishedVersion | en |
| dcterms.bibliographicCitation.doi | 10.1039/c4cp02139h | |
| dcterms.bibliographicCitation.issue | 48 | |
| dcterms.bibliographicCitation.journaltitle | Physical chemistry, chemical physics | en |
| dcterms.bibliographicCitation.originalpublishername | Royal Society of Chemistry | de |
| dcterms.bibliographicCitation.originalpublisherplace | Cambridge | de |
| dcterms.bibliographicCitation.pageend | 26623 | |
| dcterms.bibliographicCitation.pagestart | 26617 | |
| dcterms.bibliographicCitation.volume | 16 | |
| tub.accessrights.dnb | free | |
| tub.affiliation | Fak. 2 Mathematik und Naturwissenschaften::Inst. Chemie | de |
| tub.affiliation.faculty | Fak. 2 Mathematik und Naturwissenschaften | de |
| tub.affiliation.institute | Inst. Chemie | de |
| tub.publisher.universityorinstitution | Technische Universität Berlin |
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