화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.137, No.34, 10954-10957, 2015
An All-Metal Aromatic Sandwich Complex [Sb3Au3Sb3](3-)
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 "monolayered" center, but not to an all-metal species. Here, we describe the synthesis of an unprecedented all-metal aromatic sandwich complex, [Sb3Au3Sb3](3-), 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 -> Au donation and Sb <- Au back-donation) markedly redistribute the valence electrons from the cyclo-Sb-3 ligands and Au-3 interlayer to the Au-Sb bonds, which hold the complex together via sigma bonding. Each cyclo-Sb-3 possesses aromaticity with delocalized three-center three-electron (3c-3e) pi bonds, which are essentially equivalent to a 3c-4e pi pi* triplet system, following the reversed 4n Huckel rule for aromaticity in a triplet state.