Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, D-72076 Tübingen, Germany.
Dalton Trans. 2022 Dec 20;52(1):44-51. doi: 10.1039/d2dt03491c.
En route to putative rare-earth-metal alkylidene complex Li[Lu(CHSiMe)(CHSiMe)], according to Schumann's original protocol, the reaction of YCl with LiCHSiMe in a mixture of diethyl ether and -pentane afforded a neosilyl ate complex of composition LiY(CHSiMe). Tetrametallic complex LiY(CHSiMe) shows an unprecedented structural motif in the solid state and was further characterized by heteronuclear H/C/Li/Si/Y, as well as VT NMR and DRIFT spectroscopies. Analysis of the thermolysis product heteronuclear NMR spectroscopy and its reactivity towards benzophenone gave strong evidence for an alkylidene formation upon decomposition. Application of a similar protocol for the smallest rare-earth-metal scandium led to the isolation of ate complex [Li(thf)][LiSc(CHSiMe)] as the preferred crystallized product. Here, the reaction of adduct ScCl(thf) and LiCHSiMe was performed in EtO/-hexane, in the absence of additional THF. The reaction of LaCl(thf) with 3 equiv. of LiCHSiMe in THF/EtO at -40 °C yielded the ate complex [Li(thf)][La(CHSiMe)(thf)], which is the first of its kind.
在通往假定的稀土金属亚烷基配合物 Li[Lu(CHSiMe)(CHSiMe)]的途中，根据舒曼的原始方案，YCl 与 LiCHSiMe 在乙醚和戊烷的混合物中反应，得到组成 LiY(CHSiMe)的新硅基烷氧基配合物。四金属配合物 LiY(CHSiMe)在固态中表现出前所未有的结构特征，并通过异核 H/C/Li/Si/Y 以及 VT NMR 和 DRIFT 光谱进一步表征。热解产物的分析和其对二苯甲酮的反应性强烈证明了在分解时形成亚烷基。应用类似的方案用于最小的稀土金属钪，导致得到 ate 配合物 [Li(thf)][LiSc(CHSiMe)]作为首选结晶产物。在这里，在 EtO/-己烷中，在没有额外 THF 的情况下，进行 adduct ScCl(thf)和 LiCHSiMe 的反应。在-40°C 下，将 LaCl(thf)与 3 当量的 LiCHSiMe 在 THF/EtO 中反应，得到 ate 配合物[Li(thf)][La(CHSiMe)(thf)]，这是首例。
