Coinage-Metal Mediated Ring Opening of cis-1,2-Dimethoxycyclopropane: Trends from the Gold, Copper, and Silver Fischer Carbene Bond Strength.
N-heterocyclic carbene (NHC) supported coinage metal cations proved to react in the gas phase with the electron-rich cis-l,2-dimethoxycydopropane. Upon Collision Induced Dissociation (CID), several spectrometric fragment-ion signals were observed, one corresponding to the recovery of the bare cation...
| Publicado en: | Journal of the American Chemical Society Vol. 136; no. 26; pp. 9296 - 9308 |
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| Autores principales: | , |
| Formato: | Artículo |
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American Chemical Society
7/2/2014
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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=97459500&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 97459500 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: 7/2/2014 vid: 136 iid: 26 pid: 997 pub: American Chemical Society artinfo: ui: 97459500 10.1021/ja4084495 ppf: 9296 ppct: 12 formats: tig: atl: Coinage-Metal Mediated Ring Opening of cis-1,2-Dimethoxycyclopropane: Trends from the Gold, Copper, and Silver Fischer Carbene Bond Strength. aug: au: Batiste, Laurent Chen, Peter affil: Laboratorium für Organische Chemie, Eidgenössische Technische Hochschule (ETH Zürich), Vladimir-Prelog-Strasse 2, CH-8093 Zürich, Switzerland su: Carbenes Bond strengths Heterocyclic compounds Cations Gas phase reactions Density functional theory Dissociation (Chemistry) Moieties (Chemistry) sug: subj: Carbenes Bond strengths Heterocyclic compounds Cations Gas phase reactions Density functional theory Dissociation (Chemistry) Moieties (Chemistry) ab: N-heterocyclic carbene (NHC) supported coinage metal cations proved to react in the gas phase with the electron-rich cis-l,2-dimethoxycydopropane. Upon Collision Induced Dissociation (CID), several spectrometric fragment-ion signals were observed, one corresponding to the recovery of the bare cation IMes-M (IMes = l,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) and the second to the methoxymethylidene metal complex IMes—M—[HCOCH3]. The gold and copper complexes appear to stabilize the carbene sufficiently enough to promote the latter channel. On the contrary, the silver complex binds weakly to the methoxymethylidene moiety as observed by the predominance of the bare cation IMes—M channel. Density Functional Theory (DFT) investigations of the Potential Energy Surface and Bond Energy Decomposition Analyses provided results that correlate well with the experimental data. In the case of the bare cation channel, two distinct reaction pathways were found: a straightforward decoordination of the cyclopropane and a cationic rearrangement of the three-membered ring into a dimethoxypropylene isomer before dissociation. However, for the abstraction of the methoxymethylidene moiety by the metal cation, only one pathway was found. In analogy to earlier studies by other groups, we found the trend Au > Cu > Ag for the metal—carbene bond strength. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2014 holdings: @attributes: islocal: N |
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