A comprehensive theoretical study on the hydrolysis of carbonyl sulfide in the neutral water
Deng, Chao1,2; Li, Qiang-Gen1,2; Ren, Yi1,2,3; Wong, Ning-Bew3; Chu, San-Yan4; Zhu, Hua-Jie5
2008-02-01
发表期刊JOURNAL OF COMPUTATIONAL CHEMISTRY
ISSN0192-8651
卷号29期号:3页码:466-480
摘要The detailed hydration mechanism of carbonyl sulfide (COS) in the presence of up to five water molecules has been investigated at the level of HF and MP2 with the basis set of 6-311++G(d, p). The nucleophilic addition of water molecule occurs in a concerted way across the C=S bond of COS rather than across the C=O bond. This preferential reaction mechanism could be rationalized in terms of Fukui functions for the both nucleophilic and electrophilic attacks. The activation barriers, Delta H-298(not equal) for the rate-determining steps of one up to five-water hydrolyses of COS across the C=S bond are 199.4, 144.4, 123.0, 115.5, and 107.9 kJ/mol in the gas phase, respectively. The most favorable hydrolysis path of COS involves a sort of eight-membered ring transition structure and other two water molecules near to the nonreactive oxygen atom but not involved in the proton transfer, suggesting that the hydrolysis of COS can be significantly mediated by the water molecule(s) and the cooperative effects of the water molecule(s) in the nonreactive region. The catalytic effect of water molecule(s) due to the alleviation of ring strain in the proton transfer process may result from the synergistic effects of rehybridization and charge reorganization from the precoordination complex to the rate-determining transition state structure induced by water molecule. The studies on the effect of temperature on the hydrolysis of COS show that the higher temperature is unfavorable for the hydrolysis of COS. PCM solvation models almost do not modify the calculated energy barriers in a significant way. (C) 2007 Wiley Periodicals, Inc.
关键词Carbonyl Sulfide Hydrolysis Mechanism Natural Population Analysis Solvent Effects Temperature Effects
学科领域Chemistry, Multidisciplinary
DOI10.1002/jcc.20806
收录类别SCI
语种英语
WOS研究方向Chemistry
WOS类目Chemistry, Multidisciplinary
WOS记录号WOS:000252864500015
引用统计
被引频次:13[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://ir.kib.ac.cn/handle/151853/2941
专题植物化学与西部植物资源持续利用国家重点实验室
作者单位1.Sichuan Univ, Coll Chem, Chengdu 610064, Peoples R China
2.Sichuan Univ, Key State Lab Biotherapy, Chengdu 610064, Peoples R China
3.City Univ Hong Kong, Dept Biol & Chem, Kowloon, Hong Kong, Peoples R China
4.Natl Tsing Hua Univ, Dept Chem, Hsinchu 30013, Taiwan
5.Chinese Acad Sci, Kunming Inst Bot, Organ Synth & Nat Prod Lab, Kunming 650204, Peoples R China
推荐引用方式
GB/T 7714
Deng, Chao,Li, Qiang-Gen,Ren, Yi,et al. A comprehensive theoretical study on the hydrolysis of carbonyl sulfide in the neutral water[J]. JOURNAL OF COMPUTATIONAL CHEMISTRY,2008,29(3):466-480.
APA Deng, Chao,Li, Qiang-Gen,Ren, Yi,Wong, Ning-Bew,Chu, San-Yan,&Zhu, Hua-Jie.(2008).A comprehensive theoretical study on the hydrolysis of carbonyl sulfide in the neutral water.JOURNAL OF COMPUTATIONAL CHEMISTRY,29(3),466-480.
MLA Deng, Chao,et al."A comprehensive theoretical study on the hydrolysis of carbonyl sulfide in the neutral water".JOURNAL OF COMPUTATIONAL CHEMISTRY 29.3(2008):466-480.
条目包含的文件
文件名称/大小 文献类型 版本类型 开放类型 使用许可
201110180009.pdf(1162KB) 开放获取--请求全文
个性服务
推荐该条目
保存到收藏夹
查看访问统计
导出为Endnote文件
谷歌学术
谷歌学术中相似的文章
[Deng, Chao]的文章
[Li, Qiang-Gen]的文章
[Ren, Yi]的文章
百度学术
百度学术中相似的文章
[Deng, Chao]的文章
[Li, Qiang-Gen]的文章
[Ren, Yi]的文章
必应学术
必应学术中相似的文章
[Deng, Chao]的文章
[Li, Qiang-Gen]的文章
[Ren, Yi]的文章
相关权益政策
暂无数据
收藏/分享
所有评论 (0)
暂无评论
 

除非特别说明,本系统中所有内容都受版权保护,并保留所有权利。