Hydrogen bonding in CHCl3/DMSO-d(6) and CDCl3/DMSO-h(6) mixtures
Hydrogen bonding in CHCl3/DMSO-d(6) and CDCl3/DMSO-h(6) mixtures
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DOI：
10.1021/jp9623507
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发表时间：
1997-04-24
影响因子：
2.9
通讯作者：
McHale, JE
中科院分区：
文献类型：
--
作者：
Daniel, DC;McHale, JE
给出了CHCl_3/DMSO-d（6）和CDCl_3/DMSO-h（6）（DMSO二甲基亚砜）溶液的拉曼和红外光谱，并从氢键相互作用的角度进行了分析。在CHCl_3的C-H伸缩区或CDCl_3的C-D伸缩区，加入DMSO后，出现3条新的带，相对于自由的C-H或C-D伸缩区，这3条新的带被加宽和红移。我们假设，这个新的频带来自氯仿氢键DMSO和比较的相对强度的频带，由于络合和游离氯仿的两个物种的浓度的比率，根据公布的平衡常数计算。结果表明，络合作用使C-H和C-D伸缩振动的固有拉曼和红外强度显著增强。振动光谱表明，1：1和2：1（2氯仿到1 DMSO）的复合物的形式和C-H或C-D伸缩的强度增强是第一个比第二个氢键更大的证据。氢键的C-H和C-D伸缩的一般特征进行了比较，与其他氢键系统，并考虑了强度增强的可能解释。
Raman and IR spectra of solutions of CHCl3/DMSO-d(6) and CDCl3/DMSO-h(6) (DMSO dimethyl sulfoxide) solutions are presented and analyzed in terms of hydrogen-bonding interactions. In the region of the C-H stretch of CHCl3 or the C-D stretch of CDCl3, addition of DMSO causes 3 new band to appear which is broadened and red-shifted with respect to the free C-H or C-D stretch. We postulate that this new band derives from chloroform hydrogen-bonded to DMSO and compare the relative intensities of the bands due to complexed and free chloroform to the ratio of the concentrations of the two species, calculated according to published equilibrium constants. It is concluded that complexation leads to considerable enhancement of the inherent Raman and infrared intensities of the C-H and C-D stretch. The vibrational spectra reveal evidence that both 1:1 and 2:1 (2 chloroform to 1 DMSO) complexes form and that the intensity enhancement of the C-H or C-D stretch is larger for the first than the second hydrogen bond. The general features of the hydrogen-bonded C-H and C-D stretch are compared to those of other hydrogen-bonded systems, and possible explanations for the intensity enhancement are considered.