Schrenk Claudio, Gerke Birgit, Pöttgen Rainer, Clayborne Andre, Schnepf Andreas
Faculty of Science, Institute of Inorganic Chemistry, University Tübingen, Auf der Morgenstelle 18, 72076 Tübingen (Germany), Fax: (+49) 7071-29-2436.
Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstrasse 30, 48149 Münster (Germany).
Chemistry. 2015 May 26;21(22):8222-8. doi: 10.1002/chem.201500550. Epub 2015 Apr 17.
Chemistry that uses metalloid tin clusters as a starting material is of fundamental interest towards understanding the reactivity of such compounds. Since we identified {Sn10[Si(SiMe3)3]4}(2-) 7 as an ideal candidate for such reactions, we present a further step in the understanding of metalloid tin cluster chemistry. In contrast to germanium chemistry, ligand elimination seems to be a major reaction channel, which leads to the more open metalloid cluster {Sn10[Si(SiMe3)3]3}(-) 9, in which the Sn core is only shielded by three Si(SiMe3)3 ligands. Compound 9 is obtained through different routes and is crystallised together with two different countercations. Besides the structural characterisation of this novel metalloid tin cluster, the electronic structure is analysed by (119)Sn Mössbauer spectroscopy. Additionally, possible reaction pathways are discussed. The presented first step into the chemistry of metalloid tin clusters thus indicates that, with respect to metalloid germanium clusters, more reaction channels are accessible, thereby leading to a more complex reaction system.
以类金属锡簇为起始原料的化学对于理解此类化合物的反应性具有重要的基础意义。自从我们确定{Sn10[Si(SiMe3)3]4}(2-) 7是此类反应的理想候选物以来,我们在类金属锡簇化学的理解上又迈出了进一步的步伐。与锗化学不同,配体消除似乎是一个主要的反应通道,它会生成更为开放的类金属簇{Sn10[Si(SiMe3)3]3}(-) 9,其中锡核仅被三个Si(SiMe3)3配体屏蔽。化合物9可通过不同途径获得,并与两种不同的抗衡阳离子一起结晶。除了对这种新型类金属锡簇进行结构表征外,还通过(119)Sn穆斯堡尔光谱分析了其电子结构。此外,还讨论了可能的反应途径。因此,在类金属锡簇化学方面迈出的这第一步表明,相对于类金属锗簇,有更多的反应通道可供利用,从而导致一个更为复杂的反应体系。