期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 141, 期 11, 页码 4687-4695出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b13395
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资金
- state of Baden-Wurttemberg through bwHPC
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 mu-allylium-1,1-diido digold domain was best described as a three-center-four-electron bond with a pi-backbond. The valence orbitals showed extreme delocalization and strong pi-interactions between the three centers Au-1-C-1-Au-2. The bridging carbon atom C-1 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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