Transmetalation of Methyl Groups Supported by Pt--Au Bonds in the Gas Phase, in Silico, and in Solution.
We report Pt-to-Au methyl transfer reactions that occur in the gas phase and in solution. The heterobimetallic Pt/Au complexes {[(dmpe)PtMe][AuPR]} (R = Me (2a), Ph (2b), Bu (2c)), observed in the gas phase by means of electrospray ionization, were subjected to collision induced dissociation (CID) f...
| Publicado en: | Journal of the American Chemical Society Vol. 133; no. 23; pp. 8914 - 8927 |
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| Autores principales: | , , |
| Formato: | Artículo |
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American Chemical Society
6/15/2011
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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=61964408&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 61964408 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: 6/15/2011 vid: 133 iid: 23 pid: 997 pub: American Chemical Society artinfo: ui: 61964408 10.1021/ja110405q ppf: 8914 ppct: 13 formats: tig: atl: Transmetalation of Methyl Groups Supported by Pt--Au Bonds in the Gas Phase, in Silico, and in Solution. aug: au: Serra, Daniel Moret, Marc-Etienne Chen, Peter affil: Laboratorium fur Organische Chemie, Eidgenössische Technische Hochschule ETH Zurich, Wolfgang-Pauli-Strasse 10, Zurich CH-8093, Switzerland su: Methyl groups Scission (Chemistry) Electrospray ionization mass spectrometry Density functionals Dissociation (Chemistry) Chemistry sug: subj: Methyl groups Scission (Chemistry) Electrospray ionization mass spectrometry Density functionals Dissociation (Chemistry) Chemistry ab: We report Pt-to-Au methyl transfer reactions that occur in the gas phase and in solution. The heterobimetallic Pt/Au complexes {[(dmpe)PtMe][AuPR]} (R = Me (2a), Ph (2b), Bu (2c)), observed in the gas phase by means of electrospray ionization, were subjected to collision induced dissociation (CID) from which we could observe Pt-to-Au transmetalation along two reaction pathways involving formation of a Au-Me bond, analogous to those observed for the Pt/Cu complex recently reported. In the first pathway, neutral AuMe is generated with concomitant migration of PR from Au to the Pt center, forming cation [(dmpe)PtMe(PR)] (R = Me (5a) or Ph (5b)). In the second pathway, the monophosphine stays attached to the gold center, yielding cation [(dmpe)PtMe]+ (7) and RPAuMe. Quantitative energy-resolved collision induced dissociation experiments as well as density functional theory (DFT) calculations were used to investigate the potential surface involved in the transmetalation processes. Energy barriers of 22.3 and 47.9 kcal mol for the two reaction processes of 2b and of 45.4 kcal mol for the single reaction process of 2c were obtained. Parallel reactivity is observed in THF solution, allowing for a comparison of the product distributions with those observed in the gas phase, and the postulation of simple steric control of the branching ratio between the two pathways. DFT calculations at the M06-2X//BP86/TZP level were in good agreement with the experiments. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2011 holdings: @attributes: islocal: N |
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