Franz Daniel, Szilvási Tibor, Pöthig Alexander, Deiser Franziska, Inoue Shigeyoshi
Department of Chemistry, Catalysis Research Center, Institute of Silicon Chemistry, Technische Universität München, Lichtenbergstr. 4, 85748, Garching bei München, Germany.
Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, WI, 53706-1607, USA.
Chemistry. 2018 Mar 20;24(17):4283-4288. doi: 10.1002/chem.201800609. Epub 2018 Mar 1.
The enhanced electron-donor properties of the bulky bisimino ligand 1,2-(L N) -C H (1; L =1,3-bis(mesityl)-imidazolin-2-ylidene), mesityl=2,4,6-trimethylphenyl) were exploited for the stabilization of elusive electron-deficient and low-coordinate boron dication species. The reaction of 1 with PhBBr or (B(Cl)NMe ) afforded a dicationic mononuclear boron(III) complex or a dicationic dinuclear boron(II) complex, respectively (4 , 6 ). The bonding situations of 4 and 6 were examined by means of single crystal X-ray diffraction analysis, as well as theoretical methods. Significant allocation of positive charge density into the ligand system was diagnosed for both dications. However, the metalloid-centered Lewis acidity of the dications was confirmed via hydride transfer reactions.
庞大的双亚氨基配体1,2-(L N)-C H（1；L = 1,3-双（均三甲苯基）-咪唑啉-2-亚基，均三甲苯基 = 2,4,6-三甲基苯基）增强的给电子性质被用于稳定难以捉摸的缺电子和低配位硼双阳离子物种。1与PhBBr或(B(Cl)NMe )反应分别得到一个双核单核硼(III)配合物或一个双核双核硼(II)配合物(4, 6)。通过单晶X射线衍射分析以及理论方法研究了4和6的键合情况。对于这两种双阳离子，均诊断出正电荷密度大量分布到配体体系中。然而，通过氢化物转移反应证实了双阳离子以类金属为中心的路易斯酸性。
