1,1-digoldallylium complexes: diaurated allylic carbocations indicate new prospects of the coordination chemistry of carbon
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 nucleophil...
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| Main Authors: | , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
[2019]
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| In: |
Journal of the American Chemical Society
Year: 2019, Volume: 141, Issue: 11, Pages: 4687-4695 |
| ISSN: | 1520-5126 |
| DOI: | 10.1021/jacs.8b13395 |
| Online Access: | Verlag, Volltext: https://doi.org/10.1021/jacs.8b13395
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| Author Notes: | Florian F. Mulks, Patrick W. Antoni, Jürgen H. Gross, Jürgen Graf, Frank Rominger, and A. Stephen K. Hashmi (Organisch-Chemisches Institut, Heidelberg University) |
| Summary: | 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. |
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| Item Description: | Gesehen am 04.06.2019 |
| Physical Description: | Online Resource |
| ISSN: | 1520-5126 |
| DOI: | 10.1021/jacs.8b13395 |