Mechanism and thermal rate constants for complete series reactions of bromochlorophenols with H
Mechanism and thermal rate constants for complete series reactions of bromochlorophenols with H
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溴氯苯酚与 H 的完全系列反应的机理和热速率常数
DOI：
10.1039/c7ra12781b
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发表时间：
2018-01
期刊：
影响因子：
3.9
通讯作者：
Zhang Qingzhu
中科院分区：
文献类型：
--
作者：
Zheng Siyuan;Zhao Xianwei;Li Yunfeng;Xu Fei;Zhang Qingzhu
溴氯苯氧基自由基（BCPR）是形成多溴和氯化二苯并对二恶英和二苯并呋喃（PBCDD/Fs）的主要前体。采用量子化学方法在MPWB 1 K/6-311+G（3df，2 p）//MPWB 1 K/6-31+G（d，p）水平上对96种溴氯苯酚（BCP）同系物与H原子的一系列反应生成BCPRs的过程进行了研究。在600-1200 K的宽温度范围内，使用正则变分过渡态（CVT）理论沿着小曲率隧穿（SCT）贡献获得每个反应的速率常数。此外，还比较了溴代酚（BPs）和氯代酚（CPs）与H的萃取反应和BCPs与H的反应。计算结果表明，在BCP的O-H键的相对反应性似乎是辅助和主导的卤化的总程度和模式，但它似乎不是由溴和氯原子的分布。此外，邻位的卤素取代增加了BCP的稳定性并降低了O-H键的反应性。本工作为今后多溴环十二烷/呋喃的实验研究提供了参考数据。
Bromochlorophenoxy radicals (BCPRs) are the principal precursors for the formation of mixed polybrominated and chlorinated dibenzo-p-dioxins and dibenzofurans (PBCDD/Fs). In this study, the formation of BCPRs from a complete series of reactions of 96 bromochlorophenol (BCP) congeners with H atoms was analyzed using quantum chemical methods at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants of each reaction were obtained using canonical variational transition-state (CVT) theory along with a small-curvature tunneling (SCT) contribution over a wide temperature range of 600–1200 K. In addition, abstraction reactions of bromophenols (BPs) and chlorophenols (CPs) by H are compared with reactions of BCPs with H. The computational results indicate that the relative reactivity of the O–H bonds in the BCPs appears to be assisted and dominated by the total degree and pattern of halogenation, but it does not appear to be determined by the distribution of the bromine and chlorine atoms. In addition, halogen substitution at the ortho position increases the stability of the BCPs and reduces the reactivity of the O–H bonds. This work is beneficial in that it provides reference data for future experimental research into the formation of PBCDD/Fs.
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影响因子：
11.4
作者：
Qingzhu Zhang;X. Qu;Hui Wang;Fei Xu;Xiangyang Shi;Wen-xing Wang
通讯作者：
Qingzhu Zhang;X. Qu;Hui Wang;Fei Xu;Xiangyang Shi;Wen-xing Wang
影响因子：
8.8
作者：
Sim, Won-Jin;Lee, Sung-Hee;Oh, Jeong-Eun
通讯作者：
Oh, Jeong-Eun
影响因子：
11.4
作者：
Wanni Yu;Jingtian Hu;Fei Xu;Xiaoyan Sun;R. Gao;Qingzhu Zhang;Wen-xing Wang
通讯作者：
Wanni Yu;Jingtian Hu;Fei Xu;Xiaoyan Sun;R. Gao;Qingzhu Zhang;Wen-xing Wang
DOI：
10.1021/jp712168n
发表时间：
2008-04
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
M. Altarawneh;B. Dlugogorski;E. Kennedy;J. Mackie
通讯作者：
M. Altarawneh;B. Dlugogorski;E. Kennedy;J. Mackie
影响因子：
11.4
作者：
Catherine S Evans;B. Dellinger
通讯作者：
Catherine S Evans;B. Dellinger