Department of Chemistry, Technische Universität München, Munich, Germany.
Philos Trans A Math Phys Eng Sci. 2010 Mar 28;368(1915):1265-84. doi: 10.1098/rsta.2009.0270.
Homoatomic polyanions have the basic capability for a bottom-up synthesis of nanostructured materials. Therefore, the chemistry and the structures of polyhedral nine-atom clusters of tetrel elements E(9) is highlighted. The nine-atom Zintl ions are available in good quantities for E = Si-Pb as binary alkali metal (A) phases of the composition A(4)E(9) or A(12)E(17). Dissolution or extraction of the neat solids with aprotic solvents and crystallization with alkali metal-sequestering molecules or crown ethers leads to a large variety of structures containing homoatomic clusters with up to 45 E atoms. Cluster growth occurs via oxidative coupling reactions. The clusters can further act as a donor ligand in transition metal complexes, which is a first step to the formation of bimetallic clusters. The structures and some nuclear magnetic resonance spectroscopic properties of these so-called intermetalloid clusters are reviewed, with special emphasis on tetrel clusters that are endohedrally filled with transition metal atoms.
等电子多阴离子具有从下至上合成纳米结构材料的基本能力。因此，本文重点介绍了拟卤元素[E(9)]（4-）的多面体九原子团簇的化学和结构。九原子 Zintl 离子在 E = Si-Pb 中以二元碱金属（A）相 A(4)E(9)或 A(12)E(17)的形式大量存在。将纯固体用质子惰性溶剂溶解或萃取，并用碱金属隔离分子或冠醚进行结晶，可得到含有多达 45 个 E 原子的同核原子簇的多种结构。簇的生长通过氧化偶联反应发生。这些原子簇可以进一步作为过渡金属配合物中的供体配体，这是形成双金属原子簇的第一步。本文综述了这些所谓的金属间原子簇的结构和一些核磁共振波谱性质，特别强调了内部填充有过渡金属原子的拟卤原子簇。
