dc.creator | Miranda Pizarro, Juan | es |
dc.creator | Luo, Zhongwen | es |
dc.creator | Moreno Díaz, Juan José | es |
dc.creator | Dickie, Diane A. | es |
dc.creator | Campos Manzano, Jesús | es |
dc.creator | Brent Gunnoe, T. | es |
dc.date.accessioned | 2021-10-13T09:53:14Z | |
dc.date.available | 2021-10-13T09:53:14Z | |
dc.date.issued | 2021 | |
dc.identifier.citation | Miranda Pizarro, J., Luo, Z., Moreno, J.J., Dickie, D.A., Campos Manzano, J. y Brent Gunnoe, T. (2021). Reductive C–C Coupling from Molecular Au(I) Hydrocarbyl Complexes: A Mechanistic Study. Journal of the American Chemical Society, 143 (6), 2509-2522. | |
dc.identifier.issn | 1520-5126 | es |
dc.identifier.uri | https://hdl.handle.net/11441/126533 | |
dc.description.abstract | Organometallic gold complexes are used in a range of catalytic reactions, and they often serve as catalyst precursors that mediate C–C bond formation. In this study, we investigate C–C coupling to form ethane from various phosphine-ligated gem-digold(I) methyl complexes including [Au2(μ-CH3)(PMe2Ar′)2][NTf2], [Au2(μ-CH3)(XPhos)2][NTf2], and [Au2(μ-CH3)(tBuXPhos)2][NTf2] {Ar′ = C6H3-2,6-(C6H3-2,6-Me)2, C6H3-2,6-(C6H2-2,4,6-Me)2, C6H3-2,6-(C6H3-2,6-iPr)2, or C6H3-2,6-(C6H2-2,4,6-iPr)2; XPhos = 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl; tBuXPhos = 2-di-tert-butylphosphino-2′,4′,6′-triisopropylbiphenyl; NTf2 = bis(trifluoromethyl sulfonylimide)}. The gem-digold methyl complexes are synthesized through reaction between Au(CH3)L and Au(L)(NTf2) {L = phosphines listed above}. For [Au2(μ-CH3)(XPhos)2][NTf2] and [Au2(μ-CH3)(tBuXPhos)2][NTf2], solid-state X-ray structures have been elucidated. The rate of ethane formation from [Au2(μ-CH3)(PMe2Ar′)2][NTf2] increases as the steric bulk of the phosphine substituent Ar′ decreases. Monitoring the rate of ethane elimination reactions by multinuclear NMR spectroscopy provides evidence for a second-order dependence on the gem-digold methyl complexes. Using experimental and computational evidence, it is proposed that the mechanism of C–C coupling likely involves (1) cleavage of [Au2(μ-CH3)(PMe2Ar′)2][NTf2] to form Au(PR2Ar′)(NTf2) and Au(CH3)(PMe2Ar′), (2) phosphine migration from a second equivalent of [Au2(μ-CH3)(PMe2Ar′)2][NTf2] aided by binding of the Lewis acidic [Au(PMe2Ar′)]+, formed in step 1, to produce [Au2(CH3)(PMe2Ar′)][NTf2] and [Au2(PMe2Ar′)]+, and (3) recombination of [Au2(CH3)(PMe2Ar′)][NTf2] and Au(CH3)(PMe2Ar′) to eliminate ethane. | es |
dc.description.sponsorship | España, Ministerio de Ciencia e Innovación Project PID2019-110856GA-I00 | es |
dc.format | application/pdf | es |
dc.format.extent | 14 p. | es |
dc.language.iso | eng | es |
dc.publisher | American Chemical Society | es |
dc.relation.ispartof | Journal of the American Chemical Society, 143 (6), 2509-2522. | |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.title | Reductive C–C Coupling from Molecular Au(I) Hydrocarbyl Complexes: A Mechanistic Study | es |
dc.type | info:eu-repo/semantics/article | es |
dc.type.version | info:eu-repo/semantics/publishedVersion | es |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es |
dc.relation.projectID | Project PID2019-110856GA-I00 | es |
dc.relation.publisherversion | http://dx.doi.org/10.1021/jacs.0c11296 | es |
dc.identifier.doi | 10.1021/jacs.0c11296 | es |
dc.journaltitle | Journal of the American Chemical Society | es |
dc.publication.volumen | 143 | es |
dc.publication.issue | 6 | es |
dc.publication.initialPage | 2509 | es |
dc.publication.endPage | 2522 | es |
dc.contributor.funder | Ministerio de Ciencia e Innovación (MICIN). España | es |