Franke Maurice, Klingsiek Maximilian J, Buth Julian, Lamm Jan-Hendrik, Neumann Beate, Stammler Hans-Georg, Mitzel Norbert W
Universität Bielefeld, Fakultät für Chemie, Lehrstuhl für Anorganische Chemie und Strukturchemie (ACS), Centre for Molecular Materials (CM2), Universitätsstr. 25, D-33615 Bielefeld, Germany.
Dalton Trans. 2024 May 7;53(18):7751-7762. doi: 10.1039/d4dt00379a.
Hexadentate poly-Lewis acids (PLA) based on the bowl-shaped tribenzotriquinacene (TBTQ) have been synthesised. The introduction of three -propyl groups into the benzhydrylic positions of the TBTQ backbone has significantly increased the solubility of the subsequently derived compounds. Semi-flexible PLAs containing boron and aluminium were obtained by hydrometallation of the corresponding 2,3,6,7,10,11-hexaalkynyl-TBTQ. Other rigid hexadentate PLAs were synthesised by stannylation of the corresponding alkyne units with MeSnNMe followed by tin-element exchange reactions. The Lewis acidity of these PLAs was investigated in host-guest experiments with pyridine. Further experiments with bidentate bases showed correlations between their flexibility, their Lewis basicity and the complexation behaviour towards the synthesised PLAs. Addition of bis((dimethylphosphino)methyl)dimethylsilane (BisPhos) to solutions of the rigid alkynyl PLAs led to the formation of 3 : 1 adducts. Single crystal X-ray diffraction was used to further elucidate the host-guest connectivtiy. In addition, a sixfold pnictogen-bonding donor was synthesised by tin-antimony exchange.
已合成了基于碗状三苯并三萘并苯（TBTQ）的六齿多路易斯酸（PLA）。在TBTQ主链的二苯甲基位置引入三个丙基显著提高了后续衍生化合物的溶解度。通过相应的2,3,6,7,10,11-六炔基-TBTQ的氢金属化反应得到了含硼和铝的半柔性PLA。通过用MeSnNMe对相应的炔基单元进行锡化，随后进行锡-元素交换反应，合成了其他刚性六齿PLA。在与吡啶的主客体实验中研究了这些PLA的路易斯酸度。用双齿碱进行的进一步实验表明，它们的柔韧性、路易斯碱性与对合成的PLA的络合行为之间存在相关性。向刚性炔基PLA的溶液中加入双（（二甲基膦基）甲基）二甲基硅烷（BisPhos）导致形成3∶1加合物。使用单晶X射线衍射进一步阐明主客体连接性。此外，通过锡-锑交换合成了一种六重氮族元素键供体。
