Mortis Alexandros, Malzacher Jonas, Maichle-Mössmer Cäcilia, Anwander Reiner
Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany.
Chemistry. 2024 Jul 19;30(41):e202401687. doi: 10.1002/chem.202401687. Epub 2024 Jul 1.
The present study corroborates that the neutral tridentate N-ligand 1,4,7-trimethyl-triazacyclononane (MeTACN) qualifies as a versatile platform to study selective ligand exchange with rare-earth-metal alkyl complexes, herein [(MeTACN)YMe]. Treatment with Brønsted-acidic bis(dimethylsilyl)amine, HN(SiHMe), gave selectively the mono-exchanged heteroleptic complex [(MeTACN)YMe{N(SiHMe)}]. Depending on the molecular ratio employed, the reaction of [(MeTACN)YMe] with AlMe resulted in the isolation/crystallization of [(MeTACN)YMe(AlMe)] [1 : 1] or ion-separated [(MeTACN)YMe(AlMe)][AlMe] [1 : 2] and [(MeTACN)YMe(AlMe)][AlMe] [1 : 3]. Analogous reactions with the heavier group 13 methyls GaMe and InMe generated mixed methyl/tetramethylgallato complex [(MeTACN)YMe(GaMe)] and ion-separated [{(MeTACN)YMe}{μ-Me}][InMe]. Finally, dimethylalane, HAlMe, converted [(MeTACN)YMe] into heteroaluminate [(MeTACN)Y(HAlMe)], representing an AlMe-supported, molecular yttrium trihydride complex. All compounds were investigated by single crystal X-ray diffraction (SC-XRD), homo- and heteronuclear (C, Al, Y, In) NMR as well as IR spectroscopies and elemental analyses.
本研究证实，中性三齿N-配体1,4,7-三甲基-三氮杂环壬烷（MeTACN）是研究与稀土金属烷基配合物（此处为[(MeTACN)YMe]）进行选择性配体交换的通用平台。用布朗斯特酸性双（二甲基硅基）胺HN(SiHMe)处理，选择性地得到单交换杂配配合物[(MeTACN)YMe{N(SiHMe)}]。根据所用的分子比例，[(MeTACN)YMe]与AlMe反应，分离/结晶得到[(MeTACN)YMe(AlMe)] [1∶1]或离子分离的[(MeTACN)YMe(AlMe)][AlMe] [1∶2]和[(MeTACN)YMe(AlMe)][AlMe] [1∶3]。与较重的第13族甲基化合物GaMe和InMe进行类似反应，生成混合甲基/四甲基镓酸根配合物[(MeTACN)YMe(GaMe)]和离子分离的[{(MeTACN)YMe}{μ-Me}][InMe]。最后，二甲基铝HAlMe将[(MeTACN)YMe]转化为杂铝酸盐[(MeTACN)Y(HAlMe)]，这是一种由AlMe支撑的分子型三氢化钇配合物。所有化合物均通过单晶X射线衍射（SC-XRD）、同核和异核（C、Al、Y、In）NMR以及红外光谱和元素分析进行了研究。
