C(sp3)−H bond activation by vinylidene gold(I) complexes

• Verfasst von: Klein, Johannes E. M. N. [VerfasserIn]
• Verfasst von: Nunes dos Santos Comprido, Laura [VerfasserIn]
• Verfasst von: Hashmi, A. Stephen K. [VerfasserIn]
• Titel: C(sp3)−H bond activation by vinylidene gold(I) complexes
• Titelzusatz: a concerted asynchronous or stepwise process?
• Verf.angabe: Johannes E.M.N. Klein, Gerald Knizia, Laura Nunes dos Santos Comprido, Johannes Kästner and A. Stephen K. Hashmi
• Umfang: 7 S.
• Fussnoten: Version of record online: October 19, 2017 ; Gesehen am 28.06.2018 ; Im Titel ist die Zahl 3 als Hochzahl dargestellt
• Titel Quelle: Enthalten in: Chemistry - a European journal
• Jahr Quelle: 2017
• Band/Heft Quelle: 23(2017), 63, S. 16097-16103
• ISSN Quelle: 1521-3765
• DOI: doi:10.1002/chem.201703815
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1576932125

Abstract

A detailed analysis of the C(sp3)−H activation process by vinylidene AuI complexes is described based on an intrinsic bond orbital analysis. Based on our analysis this event can be divided into three phases: (i) hydride transfer, (ii) C−C bond formation, and (iii) σ to π rearrangement of the lone pair coordinated to Au. Small perturbations of the system lead to either a concerted asynchronous reaction, or a stepwise reaction featuring an intermediate with a C-H-C three-centre two-electron (3c-2e) bond. The role of π-donating substituents is highlighted and provides a way of controlling reactions of this type in future experimental studies.