Wang Liliang, Zhen Guorong, Li Yinhuan, Kira Mitsuo, Yan Liping, Chang Xiao-Yong, Huang Lu, Li Zhifang
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, 311121, Hangzhou, Zhejiang, People's Republic of China.
Department of Chemistry, Southern University of Science and Technology, 518055, Shenzhen, Guangdong, People's Republic of China.
Nat Commun. 2022 Apr 4;13(1):1785. doi: 10.1038/s41467-022-29476-1.
The bonding between gold and main-group metallic elements (M) featuring Au-M polarity, has been studied recently. The gold in the bonds is expected to have the oxidation number of -1, and hence, nucleophilic. However, the knowledge of the reactivity of the gold-metal bonds remains limited. Here, we report digold-substituted germanes of the form of R'Ge(AuPR)(AuGeR') (3a; R = Me, 3b; R = Et), featuring two Au-Ge(IV) and one Au-Ge(II) bonds. DFT calculations of 3a revealed the existence of high-lying σ(Ge-Au) type HOMO and low-lying LUMO with germylene p nature. A pendular motion of AuPR group between Ge(IV) and Ge(II) of 3 occurs in the NMR time scale, suggesting that the Ge(II) center has an enhanced electrophilicity to be attacked by the nucleophilic gold (-I) atom. 3a reacts with nucleophilic Cl and electrophilic MeOTf reagents at Ge(II) and Ge(IV) centers, respectively.
最近，人们对具有金 - 主族金属元素（M）极性的金与主族金属元素之间的键合进行了研究。键合中的金预计具有 -1 的氧化数，因此具有亲核性。然而，关于金 - 金属键反应性的认识仍然有限。在此，我们报道了 R'Ge(AuPR)(AuGeR') 形式的二金取代锗烷（3a；R = 甲基，3b；R = 乙基），其具有两个金 - 锗（IV）键和一个金 - 锗（II）键。对 3a 的密度泛函理论计算表明存在高位的 σ(Ge - Au) 型最高占据分子轨道（HOMO）和低位的具有亚锗烯 p 性质的最低未占据分子轨道（LUMO）。在核磁共振（NMR）时间尺度上，3 中 AuPR 基团在锗（IV）和锗（II）之间发生摆动运动，这表明锗（II）中心具有增强的亲电性，可被亲核性的金（-I）原子攻击。3a 分别在锗（II）和锗（IV）中心与亲核性的 Cl 和亲电性的三氟甲磺酸甲酯（MeOTf）试剂发生反应。
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