Density Functional Theory Investigation of the Reaction of the Chlorine Atom-Carbon Disulfide Molecular Complex with Dimethylbutane: Implications for Tertiary Selectivity in Alkane Photochlorination Reactions

Dongqi Wang; David Lee Phillips; Wei-Hai Fang

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Density Functional Theory Investigation of the Reaction of the Chlorine Atom-Carbon Disulfide Molecular Complex with Dimethylbutane: Implications for Tertiary Selectivity in Alkane Photochlorination Reactions

机译：氯原子-碳二硫化物分子配合物与二甲基丁烷反应的密度泛函理论研究：烷烃光氯化反应中三级选择性的意义

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We report a density functional theory (DFT) investigation of the chemical reactivity of the S = C = S … Cl complex toward 2,3-dimethylbutane (DMB) and compare it to the related reaction of a Cl atom with DMB. The DFT calculations predict that the reaction of a Cl atom with DMB will have little tertiary selectivity toward chlorination consistent with experimental results for photochlorination of alkanes in inert solvents. However, the DFT calculations indicate that the reaction of the S = C = S … Cl complex with DMB is different with the primary H abstraction reaction being noticeably more difficult than the tertiary H abstraction reaction. This indicates there will be significant tertiary selectivity for the reaction of the S = C = S … Cl complex with DMB and this is consistent with experimental results for chlorination of DMB in CS_2 solvent. We examine the reaction mechanism and properties of the S = C = S … Cl complex and explore potential implications for tertiary selectivity for other related photochlorination reactions.

机译：我们报告了密度泛函理论（DFT），研究了S = C = S…Cl络合物对2,3-二甲基丁烷（DMB）的化学反应性，并将其与Cl原子与DMB的相关反应进行了比较。 DFT计算预测，Cl原子与DMB的反应对氯化的叔选择性几乎没有，这与惰性溶剂中烷烃光氯化的实验结果一致。但是，DFT计算表明，S = C = S…Cl络合物与DMB的反应不同，伯H提取反应明显比叔H提取反应困难。这表明S = C = S…Cl络合物与DMB的反应将具有显着的三级选择性，这与在CS_2溶剂中DMB氯化的实验结果一致。我们研究了S = C = S…Cl配合物的反应机理和性质，并探讨了对其他相关光氯化反应的三次选择性的潜在影响。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2003年第10期|共6页
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Dongqi Wang; David Lee Phillips; Wei-Hai Fang;
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中图分类物理化学（理论化学）、化学物理学;
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1. Density Functional Theory Investigation of the Reaction of the Chlorine Atom-Carbon Disulfide Molecular Complex with Dimethylbutane: Implications for Tertiary Selectivity in Alkane Photochlorination Reactions [J] . Dongqi Wang, David Lee Phillips, Wei-Hai Fang The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2003,第10期

机译：氯原子-碳二硫化物分子配合物与二甲基丁烷反应的密度泛函理论研究：烷烃光氯化反应中三级选择性的意义
2. Density functional theory investigation of electrophilic addition reaction of chlorine to tricyclo[4.2.2.2~(2,5)]dodeca-1,5-diene [J] . Rza ABBASOGLU, Ahmet YASAR Turkish journal of chemistry . 2010,第1期

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3. Density functional theory investigation of electrophilic addition reaction of chlorine to tricyclo[4.2.2.2^{2,5}]dodeca-1,5-diene [J] . RZA ABBASO?LU, AHMET YA?AR Turkish journal of chemistry . 2010,第1期

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4. Mechanisms of Reactions Related to Selective Alkane Oxidation by Pt Complexes [C] . Jennifer L. Look, Ulrich Fekl, Karen I. Goldberg ACS Symposium Series 885; American Chemical Society(ACS) National Meeting; 2002; Orlando,FL(US) . 2002

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Density Functional Theory Investigation of the Reaction of the Chlorine Atom-Carbon Disulfide Molecular Complex with Dimethylbutane: Implications for Tertiary Selectivity in Alkane Photochlorination Reactions

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