1,1-Digoldallylium Complexes: Diaurated Allylic Carbocations Indicate New Prospects of the Coordination Chemistry of Carbon,Journal of the American Chemical Society

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1,1-Digoldallylium Complexes: Diaurated Allylic Carbocations Indicate New Prospects of the Coordination Chemistry of Carbon
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-02-14 , DOI: 10.1021/jacs.8b13395
Florian F Mulks ₁ , Patrick W Antoni ₁ , Jürgen H Gross ₁ , Jürgen Graf ₁ , Frank Rominger ₁ , A Stephen K Hashmi ₁

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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.

中文翻译：

1,1-Digoldallylium 络合物：Diauated 烯丙基碳正离子显示碳配位化学的新前景

(NHC)(环丙烯基)金(I)络合物与阳离子金络合物[(IPr)AuX]反应得到极活泼的烯丙基-1,1-二基桥接二金中间体。我们通过 FT-ICR-MS/MS、NMR 和 UV-vis-NIR 实验证明了该结构的存在和构成，并分离了亲核加成产物 [(Me)(Ph)(CCHC){Au(IPr)}2 (SOMe2)]NTf2 与 DMSO。我们的计算研究表明，这种 μ-allylium-1,1-diido 二元结构域的键合情况最好描述为具有 π-backbond 的三中心四电子键。价轨道表现出极端的离域和三个中心 Au1-C1-Au2 之间的强 π 相互作用。在这种结构中，桥接碳原子 C1 最好被描述为三角平面 sp 杂化碳。

更新日期：2019-02-14

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