Lebon Jakob, Beauvois Maxime, Maichle-Mössmer Cäcilia, Sirsch Peter, Anwander Reiner
Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany.
Chemistry. 2024 Dec 23;30(72):e202403472. doi: 10.1002/chem.202403472. Epub 2024 Nov 13.
Utilizing ternary mixtures [LnMe]/K(2,4-dtbp)/GaMe (Ln=Lu, Y; 2,4-dtbp=2,4-di-tert-butyl-pentadienyl), a series of metallacycles is accessible via tandem salt metathesis/deprotonation. Depending on the precursor molar ratio, both gallatabenzene and lutetacyclic moieties with fully planar metallacycles are obtained, which were further analyzed using DFT calculations. The precursor molar ratio affects the extent of pentadienyl C-H-bond activation and oligomerization to tetra- and pentametallic arrays. Reacting a 1 : 2 : 2 mixture at -40 °C gave the open sandwich methyl complex (2,4-dtbp)Lu(CH), displaying a vital intermediate for subsequent ring-closure reactions.
利用三元混合物[LnMe]/K(2,4 - dtbp)/GaMe（Ln = Lu、Y；2,4 - dtbp = 2,4 - 二叔丁基戊二烯基），通过串联盐复分解/去质子化反应可得到一系列金属环。根据前体的摩尔比，可得到镓苯和具有完全平面金属环的镥环部分，并用密度泛函理论计算对其进行了进一步分析。前体摩尔比会影响戊二烯基C - H键活化以及寡聚形成四金属和五金属阵列的程度。在 - 40°C下使1∶2∶2的混合物反应，得到开式夹心甲基配合物(2,4 - dtbp)Lu(CH)，它是后续闭环反应的关键中间体。
