Schorpp Marcel, Krossing Ingo
Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg, Albertstr. 21, 79104, Freiburg, Germany.
Chemistry. 2020 Nov 6;26(62):14109-14117. doi: 10.1002/chem.202002932. Epub 2020 Oct 1.
Heterobimetallic cationic sandwich complexes [M(μ-Cp)M'Cp] of group 13 (M=Ga, In) and group 14 (M'=Ge, Sn) elements have been prepared as [WCA] salts (WCA=Al(OR ) ; OR =OC(CF ) ). Their molecular structures include free apical gallium or indium atoms. The sandwich complexes were formed in the reactions of [M(HMB)] [WCA] (HMB=C Me ) with the free metallocenes [M'Cp ]. Their structures are related to known stannocene and stannocenium salts; the unprecedented germanium analogues, namely the free germanocenium cation [GeCp] and the corresponding triple-decker complex cation [CpGe(μ-Cp)GeCp] , are described herein. By variation of the reaction conditions, these sandwich complexes can be transformed into the group 13/14 mixed cationic coordination polymer [{In(HMB)(μ-SnCp )} ][WCA] . This polymeric chain motif was also successfully replicated by the synthesis of complexes [{Ga/In(HMB)(μ-FeCp )} ][WCA] containing FeCp as a bridging ligand.
已制备出第13族（M = Ga、In）和第14族（M' = Ge、Sn）元素的异双金属阳离子夹心配合物[M(μ-Cp)M'Cp]，以[WCA]盐（WCA = Al(OR)₄；OR = OC(CF₃)₃）的形式存在。它们的分子结构包含游离的顶端镓或铟原子。夹心配合物是在[M(HMB)]₂[WCA]（HMB = C₆Me₆）与游离茂金属[M'Cp₂]的反应中形成的。它们的结构与已知的二茂锡和二茂锡鎓盐相关；本文描述了前所未有的锗类似物，即游离的锗茂鎓阳离子[GeCp₂]⁺和相应的三层夹心配合物阳离子[Cp₂Ge(μ-Cp)GeCp₂]²⁺。通过改变反应条件，这些夹心配合物可以转化为第13/14族混合阳离子配位聚合物[{In(HMB)(μ-SnCp₂)}₂][WCA]₂。通过合成含有FeCp₂作为桥连配体的配合物[{Ga/In(HMB)(μ-FeCp₂)}₂][WCA]₂，也成功复制了这种聚合物链结构单元。
