Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35032, Marburg, Germany.
Institute of Nanotechnology, Karlsruher Institute of Technologie (KIT), Campus North, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.
Angew Chem Int Ed Engl. 2017 Oct 16;56(43):13253-13258. doi: 10.1002/anie.201707632. Epub 2017 Sep 13.
Reactions of [K(crypt-222)] (TlBi )⋅0.5 en (1 b) with [Ru(cod)(H CC(Me)CH ) ] (A) in 1,2-diaminoethane (en) led to the formation of two compounds with new bismuth-rich cluster anions, [K(crypt-222)] [Bi {Ru(cod)} ]⋅1.5 en (2) and [K(crypt-222)] [Tl Bi {Ru(cod)}]⋅2 tol (3), alongside the salt of a binary nido cluster, [K(crypt-222)] (Tl Bi )⋅2 en (4). The anions in 2 and 3 are two further examples of rare heterometallic clusters containing Ru atoms. As one cod ligand is retained on each Ru atom in both clusters, the anions may be viewed as intermediates on the way towards larger, ligand-free intermetalloid clusters. Quantum-chemical studies provided insight into the bonding situation in these clusters. According to these studies, the anion of 2 features both electron-precise and electron-deficient parts. Electrospray ionization mass spectrometry analysis indicated that the clusters undergo stepwise fragmentation.
[K(crypt-222)] (TlBi )⋅0.5 en（1b）与[Ru(cod)(HCC(Me)CH ) ]（A）在 1,2-二氨基乙烷（en）中的反应导致了两种具有新的富铋簇阴离子的化合物的形成，[K(crypt-222)] [Bi{Ru(cod)}]⋅1.5 en（2）和[K(crypt-222)] [TlBi{Ru(cod)}]⋅2 tol（3），以及二元 nido 簇的盐[K(crypt-222)] (TlBi )⋅2 en（4）。2 和 3 中的阴离子是另外两个含有 Ru 原子的罕见杂金属簇的例子。由于每个 Ru 原子上保留了一个 cod 配体，因此这些阴离子可以被视为更大的、无配体的金属间簇的中间体。量子化学研究提供了对这些簇中键合情况的深入了解。根据这些研究，2 的阴离子具有电子精确和电子缺乏两部分。电喷雾电离质谱分析表明，这些簇经历逐步碎片化。
