Monoorganobismuth(III) dihalides containing the new pincer 2,6-{MeN(CH2CH2)2NCH2}2C6H3 ligand: solution NMR, vibrational and single-crystal X-ray studies.
Monoorganobismuth(III) dihalides containing the new pincer 2,6-{MeN(CH2CH2)2NCH2}2C6H3 ligand: solution NMR, vibrational and single-crystal X-ray studies.
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含有新型钳形 2,6-{MeN(CH2CH2)2NCH2}2C6H3 配体的单有机铋 (III) 二卤化物：溶液 NMR、振动和单晶 X 射线研究。
DOI：
10.1039/b811713f
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发表时间：
2009
影响因子：
4
通讯作者：
C. Silvestru
中科院分区：
文献类型：
--
作者：
A. Soran;H. Breunig;V. Lippolis;M. Arca;C. Silvestru
RLi [R = 2，6-{MeN（CH_2CH_2）_2NCH_2}_2C_6 H_3]与BiCl_3（摩尔比1：1）反应得到RBiCl_2（2）。通过卤素交换反应从2得到RBiBr 2（3）和RBiI 2（4）。在溶液和固体状态下表征了含有新的空间要求（N，C，N）-钳形配体的有机铋（III）二卤化物。通过单晶X射线衍射确定了化合物的分子结构。它们都显示出T形的CBiX（2）核心，通过两个相互反式的分子内N->Bi相互作用来稳定。整个（N，C，N）BiX 2核呈现扭曲的四方锥配位几何结构。核磁共振研究也为溶液中氮铋配位的存在提供了证据。用密度泛函理论（DFT）计算了[2，6-（R（2）NCH（2））（2）C（6）H（3）]BiX（2）（R = H，Me; X = Cl，Br，I）的成键性质和振动光谱特征.
The reaction of RLi [R = 2,6-{MeN(CH2CH2)2NCH2}2C6H3 ] with BiCl3 (1:1 molar ratio) afforded RBiCl2 (2). RBiBr2 (3) and RBiI2 (4) were obtained by halogen-exchange reactions from 2 . The organobismuth(III) dihalides containing the new steric demanding (N,C,N)-pincer ligand were characterized both in solution and solid state. The molecular structures of compounds were established by single-crystal X-ray diffraction. They all show a T-shaped CBiX(2) core, stabilized by two strong intramolecular N-->Bi interactions in trans positions to each other. The overall (N,C,N)BiX2 core exhibits a distorted square-pyramidal coordination geometry. The NMR studies provided evidences for the presence of internal nitrogen-bismuth coordination in solution too. DFT calculations were performed on the related species [2,6-(R(2)NCH(2))(2)C(6)H(3)]BiX(2) (R = H, Me; X = Cl, Br, I) in order to elucidate the bond nature and vibrational spectroscopic features of these compounds.