New route to 1-thia-closo-dodecaborane(11), closo-1-SB11H11, and its halogenation reactions. The effect of the halogen on the dipole moments and the NMR spectra and the importance of spin-orbit coupling for the 11B chemical shifts.
New route to 1-thia-closo-dodecaborane(11), closo-1-SB11H11, and its halogenation reactions. The effect of the halogen on the dipole moments and the NMR spectra and the importance of spin-orbit coupling for the 11B chemical shifts.
复制标题
1-硫杂-closo-十二硼烷(11)、closo-1-SB11H11 及其卤化反应的新路线。
DOI：
10.1039/b512345c
复制
发表时间：
2006
影响因子：
4
通讯作者：
B. Štíbr
中科院分区：
文献类型：
--
作者：
J. Macháček;J. Plešek;J. Holub;D. Hnyk;V. Všetečka;I. Císařová;M. Kaupp;B. Štíbr
巢状结构-B10 H14（1）与元素硫在CHCl 3中在Et 3 N存在下在室温下反应，随后在170-190 ℃下用Et3N.BH3处理，导致以50%产率分离出Closo-1-SB 11 H11（2）。化合物的选择性亲电卤化反应导致一系列通式为12-X-closo-1-SB_（11）H_（10）（12-X-，其中X = Cl，Br和I）的单卤代衍生物的分离。通过X射线衍射分析确定了12-Cl-和12-I-的结构，并在RMP 2（fc）/6- 31 G * 水平上对所有化合物的结构进行了几何优化。所有化合物的结构与质谱和多核（1H和11B）光谱的结果一致，并辅以二维[11B-11B]-COSY和1H{11B（选择性）} NMR测量。实验11 B化学位移一般显示出可接受的协议与GIAO方法计算的理论值，但自旋轨道耦合必须包括轴承重原子取代基，如Br或I的核。确定的B12-X键的偶极矩显示出与脂肪族C-X键的相似性，并明确证实了SB 11笼中的B12 --> S偶极矩取向。
Reaction between nido-B10H14 (1) and elemental sulfur in CHCl3 in the presence of Et3N at room temperature, followed by treatment with Et3N.BH3 at 170-190 degrees C, resulted in the isolation of closo-1-SB11H11 (2) in 50% yield. Selected electrophilic halogenation reactions of compound led to the isolation of a series of monohalogenated derivatives of general constitution 12-X-closo-1-SB11H10 (12-X-, where X = Cl, Br, and I). The structures of 12-Cl- and 12-I- were determined by an X-ray diffraction analysis and the structures of all compounds were geometry optimised at the RMP2(fc)/6-31G* level. The constitution of all compounds is consistent with the results of mass spectrometry and multinuclear (1H and 11B) spectroscopy complemented by two-dimensional [11B-11B]-COSY and 1H{11B(selective)} NMR measurements. Experimental 11B chemical shifts generally show acceptable agreement with theoretical values calculated by GIAO methods, but spin-orbit coupling must be included for nuclei bearing heavy-atom substituents such as Br or I. The dipole moments determined for the B12-X bonds show similarities to those of aliphatic C-X bonds and confirm unambiguously the B12 --> S dipole moment orientation in the SB11 cage.