1,1-digoldallylium complexes

• Verfasst von: Mulks, Florian [VerfasserIn]
• Verfasst von: Antoni, Patrick W. [VerfasserIn]
• Verfasst von: Gross, Jürgen H. [VerfasserIn]
• Verfasst von: Graf, Jürgen [VerfasserIn]
• Verfasst von: Rominger, Frank [VerfasserIn]
• Verfasst von: Hashmi, A. Stephen K. [VerfasserIn]
• Titel: 1,1-digoldallylium complexes
• Titelzusatz: diaurated allylic carbocations indicate new prospects of the coordination chemistry of carbon
• Verf.angabe: Florian F. Mulks, Patrick W. Antoni, Jürgen H. Gross, Jürgen Graf, Frank Rominger, and A. Stephen K. Hashmi (Organisch-Chemisches Institut, Heidelberg University)
• E-Jahr: 2019
• Jahr: [2019]
• Umfang: 9 S.
• Illustrationen: Illustrationen
• Fussnoten: Gesehen am 04.06.2019
• Titel Quelle: Enthalten in: American Chemical SocietyJournal of the American Chemical Society
• Ort Quelle: Washington, DC : American Chemical Society, 1879
• Jahr Quelle: 2019
• Band/Heft Quelle: 141(2019), 11, Seite 4687-4695
• ISSN Quelle: 1520-5126
• DOI: doi:10.1021/jacs.8b13395
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1666660795

Abstract

Reacting (NHC)(cyclopropenyl)gold(I) complexes with cationic gold complexes [(IPr)AuX] afforded extremely reactive allylium-1,1-diido-bridged digold intermediates. We prove the existence and constitution of this structure with FT-ICR-MS/MS, NMR, and UV-vis-NIR experiments and isolated the nucleophilic addition product [(Me)(Ph)(CCHC){Au(IPr)}2(SOMe2)]NTf2 with DMSO. Our computational investigation unveiled that the bonding situation of this μ-allylium-1,1-diido digold domain was best described as a three-center-four-electron bond with a π-backbond. The valence orbitals showed extreme delocalization and strong π-interactions between the three centers Au1-C1-Au2. The bridging carbon atom C1 was best described as trigonal planar sp-hybridized carbon in this structure. Excitation succeeded in UV-vis-NIR measurements with energies as low as near-IR radiation.