Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany).
Chemistry. 2013 Nov 11;19(46):15745-58. doi: 10.1002/chem.201302931. Epub 2013 Oct 7.
Carba-closo-dodecaborate anions with two functional groups have been synthesized via a simple two-step procedure starting from monoamino-functionalized {closo-1-CB11 } clusters. Iodination at the antipodal boron atom provided access to 1-H2 N-12-I-closo-1-CB11 H10 (1 a) and 2-H2 N-12-I-closo-1-CB11 H10 (2 a), which have been transformed into the anions 1-H2 N-12-RCC-closo-1-CB11 H10 (R=H (1 b), Ph (1 c), Et3 Si (1 d)) and 2-H2 N-12-RCC-closo-1-CB11 H10 (R=H (2 b), Ph (2 c), Et3 Si (2 d)) by microwave-assisted Kumada-type cross-coupling reactions. The syntheses of the inner salts 1-Me3 N-12-RCC-closo-1-CB11 H10 (R=H (1 e), Et3 Si (1 f)) and 2-Me3 N-12-RCC-closo-1-CB11 H10 (R=H (2 e), Et3 Si (2 f)) are the first examples for a further derivatization of the new anions. All {closo-1-CB11 } clusters have been characterized by multinuclear NMR and vibrational spectroscopy as well as by mass spectrometry. The crystal structures of Cs1 a, [Et4 N]2 a, K1 b, [Et4 N]1 c, [Et4 N]2 c, 1 e, and [Et4 N][1-H2 N-2-F-12-I-closo-1-CB11 H9 ]⋅0.5 H2 O ([Et4 N]4 a⋅0.5 H2 O) have been determined. Experimental spectroscopic data and especially spectroscopic data and bond properties derived from DFT calculations provide some information on the importance of inductive and resonance-type effects for the transfer of electronic effects through the {closo-1-CB11 } cage.
通过从单氨基官能化的{closo-1-CB11}簇开始的简单两步法合成了具有两个官能团的碳硼 closo-十二硼酸盐阴离子。在对映体硼原子上的碘化作用提供了[1-H2N-12-I-closo-1-CB11H10]-（1a）和[2-H2N-12-I-closo-1-CB11H10]-（2a）的途径，它们已转化为阴离子[1-H2N-12-RCC-closo-1-CB11H10]-（R=H（1b），Ph（1c），Et3Si（1d））和[2-H2N-12-RCC-closo-1-CB11H10]-（R=H（2b），Ph（2c），Et3Si（2d））通过微波辅助 Kumada 型交叉偶联反应。内盐 1-Me3N-12-RCC-closo-1-CB11H10（R=H（1e），Et3Si（1f））和 2-Me3N-12-RCC-closo-1-CB11H10（R=H（2e），Et3Si（2f））的合成是对新阴离子进一步衍生化的首例。所有{closo-1-CB11}簇均通过多核 NMR 和振动光谱以及质谱进行了表征。Cs1a，[Et4N]2a，K1b，[Et4N]1c，[Et4N]2c，1e和[Et4N][1-H2N-2-F-12-I-closo-1-CB11H9]⋅0.5H2O（[Et4N]4a⋅0.5H2O）的晶体结构已确定。实验光谱数据，尤其是来自 DFT 计算的光谱数据和键性质，为通过{closo-1-CB11}笼传递电子效应的诱导和共振型效应的重要性提供了一些信息。
