Isolation of a Three-Coordinate Boron Cation with a Boron-Sulfur Double Bond

被引:60
作者
Franz, Daniel [1 ]
Irran, Elisabeth [1 ]
Inoue, Shigeyoshi [1 ]
机构
[1] Tech Univ Berlin, Inst Chem, D-10623 Berlin, Germany
关键词
boron; cations; hydrides; multiple bonds; sulfur; FRUSTRATED LEWIS PAIRS; B-H BOND; BORENIUM CATIONS; FACILE SYNTHESIS; COMPLEXES; IMIDAZOLIN-2-IMINATO; CHEMISTRY; REACTIVITY; LIGANDS; ACID;
D O I
10.1002/anie.201407809
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The reaction of the bulky bis(imidazolin-2-iminato) ligand precursor (1,2-((LNH)-N-Mes)(2)-C2H4)[OTs](2) (1(2+) 2[OTs](-); L-Mes = 1,3-dimesityl imidazolin-2-ylidene, OTs = p-toluenesulfonate) with lithium borohydride yields the boronium dihydride cation (1,2-((LN)-N-Mes)(2)-C2H4)BH2[OTs] (2(+) [OTs](-)). The boronium cation 2(+) [OTs](-) reacts with elemental sulfur to give the thioxoborane salt (1,2-((LN)-N-Mes)(2)-C2H4)BS[OTs] (3(+) [OTs](-)). The hitherto unknown compounds 1(2+) 2[OTs](-), 2(+)[OTs](-), and 3(+) [OTs](-) were fully characterized by spectroscopic methods and single-crystal X-ray diffraction. Moreover, DFT calculations were carried out to elucidate the bonding situation in 2(+) and 3(+). The theoretical, as well as crystallographic studies reveal that 3(+) is the first example for a stable cationic complex of three-coordinate boron that bears a B=S double bond.
引用
收藏
页码:14264 / 14268
页数:5
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