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路易斯酸碱加合物:甲酰胺与二甲基亚砜混合物的定量拉曼分析

Lewis acid-base adducts: a quantitative Raman analysis of formamide and dimethylsulfoxide mixtures.

作者信息

Alves Wagner A, Antunes Octavio A C

机构信息

Departamento de Química, Instituto de Ciências Exatas, Universidade Federal Rural do Rio de Janeiro, Rodovia BR 465/Km 7, Seropédica, RJ 23890-000, Brazil.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2007 Jul;67(3-4):847-51. doi: 10.1016/j.saa.2006.08.042. Epub 2006 Sep 5.

Abstract

Raman spectra of pure liquid dimethylsulfoxide (DMSO) and of binary mixtures of formamide (FA) and DMSO in different compositions were obtained. The vibrations involving the SO functional group in the band envelope at ca. 1050 cm(-1) of pure liquid DMSO are assigned to monomers, dimers and higher aggregates of DMSO. The appearance of a new band at 1024 cm(-1), whose intensity shows large dependence on the FA concentration, is assigned to a FA-DMSO adduct. This has been possible due to the two H-bond donor sites of FA and the strong donor character of DMSO that become the environment propitious for the donor-acceptor reaction. Quantitative analysis performed in the SO stretching region in the binary mixtures gives a 1:1 stoichiometry in this adduct in the limit of infinite dilution. This proportion is in full agreement with our previous determination for the FA-ACN adduct. The experimental evidence of the 1:1 FA-DMSO adduct is presented for the first time using Raman spectroscopy. The results described here open new possibilities to study the acid-base reactions nature of FA adducts.

摘要

获得了纯液态二甲基亚砜(DMSO)以及不同组成的甲酰胺(FA)与DMSO二元混合物的拉曼光谱。在纯液态DMSO约1050 cm⁻¹谱带包络中涉及SO官能团的振动归因于DMSO的单体、二聚体和更高聚集体。在1024 cm⁻¹处出现的一个新谱带,其强度对FA浓度有很大依赖性,归因于FA - DMSO加合物。这是由于FA的两个氢键供体位点以及DMSO的强供体特性,为供体 - 受体反应创造了有利环境。在二元混合物的SO伸缩区域进行的定量分析表明,在无限稀释极限下该加合物的化学计量比为1:1。该比例与我们之前对FA - ACN加合物的测定完全一致。首次使用拉曼光谱给出了1:1 FA - DMSO加合物的实验证据。这里描述的结果为研究FA加合物的酸碱反应性质开辟了新的可能性。

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