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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Observation of Two Conformers of Acrylic Sulfuric Anhydride by Microwave Spectroscopy
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Observation of Two Conformers of Acrylic Sulfuric Anhydride by Microwave Spectroscopy

机译：微波光谱观察丙烯酸硫酸二甲酸酐的两种

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The rotational spectrum of acrylic sulfuric anhydride (CH2=CHCOOSO2OH, AcrSA) has been observed using pulsed-nozzle Fourier transform microwave spectroscopy. The species was produced from the reaction between acrylic acid and sulfur trioxide in a supersonic jet. Spectroscopic constants are reported for both the s-cis- and s-trans-AcrSA conformers of the parent and monodeuterated (OD) isotopologues. Geometries were optimized for both conformers using M06-2X/6-311++G(3df,3pd) methods. Single-point energy calculations at the M06-2X geometries were calculated using the CCSD(T)/complete basis set method with double and triple extrapolation [CBS(D-T)]. Further calculations indicate that the anhydride results from a pi(2) + pi(2) + sigma(2) cycloaddition reaction within the acrylic acidSO(3) complex. Because the C=O double bond of the acrylic acid migrates from one of the COOH oxygens to the other during the reaction, the s-cis form of acrylic acid leads to the s-trans form of the anhydride and vice versa. With zero-point energy corrections applied to the CCSD(T) energies, the s-cis and s-trans forms of CH2-CHCOOSO2OH are 19.0 and 18.8 kcal/mol lower in energy than that of SO3 + their corresponding CH2=CHCOOH precursor conformation. The zero-point-corrected transition state energies for formation of the s-trans and s-cis anhydrides are 0.22 and 0.33 kcal/mol lower than those of the complexes of SO3 with s-cis and s-trans acrylic acid, respectively, indicating that the reaction is essentially barrierless. This system adds to a growing body of examples demonstrating that carboxylic acids readily add to SO3 in the gas phase to produce the corresponding carboxylic sulfuric anhydride.
机译：使用脉冲喷嘴傅里叶变换微波光谱观察丙烯酸硫酸酐（CH2 = ChCoOSO 2 OH，ACRSA）的旋转光谱。该物种是由超声波射流中丙烯酸和三氧化硫之间的反应产生的。据报道，母体和单型化（OD）同位素的S-CIS-和S-TRASS-ACRSA符合子的S-CIS-和S-TRASS-ACRSA符合子。使用M06-2X / 6-311 ++ G（3DF，3PD）方法针对符合子进行优化的几何形状。使用具有双重和三重外推的CCSD（T）/完整的基础集方法计算M06-2X几何的单点能量计算[CBS（D-T）]。进一步的计算表明酸酐由丙烯酸酸（3）复合物内的PI（2）+ Pi（2）+σ（2）环加成反应产生。因为丙烯酸的C = O双键在反应过程中从一个COOH氧合迁移到另一个COOH氧，S-CIS形式的丙烯酸导致酸酐的S-Trans形式，反之亦然。零点能量校正施加到CCSD（T）能量，CH2-CHCOOSO 2 OH的S-CIS和S-TRUME形式为19.0和18.8kcal /摩尔的能量低于SO3 +其相应的CH2 = CHCOOH前体构象。用于形成S-Trans和S-CIS酸酐的零点校正的过渡状态能量分别比SO3与S-CIS和S-转丙烯酸的复合物低0.22和0.33kcal / mol，表明反应基本上是障碍物。该系统增加了越来越多的实施例，示出了在气相中容易加入到SO 3的羧酸，以产生相应的羧酸硫酸酐。

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