An All-Metal Aromatic Sandwich Complex [Sb3Au3Sb3]3鈥?/sup>

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• 作者：Fu-Xing Pan ; Lei-Jiao Li ; Ying-Jin Wang ; Jin-Chang Guo ; Hua-Jin Zhai ; Li Xu ; Zhong-Ming Sun
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：September 2, 2015
• 年：2015
• 卷：137
• 期：34
• 页码：10954-10957
• 全文大小：291K
• ISSN：1520-5126

文摘

A sandwich complex, as exemplified by ferrocene in the 1950s, usually refers to one metal center bound by two arene ligands. The subject has subsequently been extended to carbon-free aromatic ligands and multiple-metal-atom 鈥渕onolayered鈥?center, but not to an all-metal species. Here, we describe the synthesis of an unprecedented all-metal aromatic sandwich complex, [Sb₃Au₃Sb₃]^{3鈥?/sup>, which was isolated as K([2.2.2]crypt)+ salt and identified by single-crystal X-ray diffraction. Quantum chemical calculations indicate that intramolecular electron transfers for the three metallic layers (Sb 鈫?Au donation and Sb 鈫?Au back-donation) markedly redistribute the valence electrons from the cyclo-Sb₃ ligands and Au₃ interlayer to the Au鈥揝b bonds, which hold the complex together via 蟽 bonding. Each cyclo-Sb₃ possesses aromaticity with delocalized three-center three-electron (3c-3e) 蟺 bonds, which are essentially equivalent to a 3c-4e 蟺蟺* triplet system, following the reversed 4n H眉ckel rule for aromaticity in a triplet state.}