On the origin of decomposition of triphenyl phosphite ozonide accelerated by ammonia or pyridine water solution | |
Liu, Jianbiao1; Chen, Dezhan1; Zhang, Guiqiu1; Zhang, Yuhua1; Zhang, Honghong1; Mi, Shizhen1; Shen, Guanlin2 | |
刊名 | journal of molecular structure-theochem |
2010-05-30 | |
卷号 | 948期号:1-3页码:71-77 |
关键词 | Hydroxide accelerated Nucleophilic addition Triphenyl phosphite ozonide Solvent effect Highest occupied molecular orbital (HOMO) |
英文摘要 | the decomposition of triphenyl phosphite ozonide (tppo) has been well recognized as a potential source of singlet oxygen (o(2), (1)delta(g)) for the chemical oxygen-iodine laser. experimental observations suggested that ammonia or pyridine water solution can accelerate the decomposition of tppo, and hydroxyl ion is responsible for accelerating singlet oxygen liberation during this decomposition. in this paper, we studied the mechanism of oh(-)-accelerated reaction using density functional theory (dft) at b3lyp/6-31+g(*) levels of theory. the calculations reveal a favorable free energy pathway for hydroxide-accelerated decomposition of tppo, i.e. nucleophilic addition at phosphorus, followed by elimination of phenoxy group and subsequent liberation of singlet oxygen. the solvent effects were studied using a polarizable continuum model. the frontier molecular orbitals of the ozonides, atom-atom wiberg bond index and corresponding atomic charges were also investigated to shed further light on the reaction pathway. (c) 2010 elsevier b.v. all rights reserved. |
WOS标题词 | science & technology ; physical sciences |
类目[WOS] | chemistry, physical |
研究领域[WOS] | chemistry |
关键词[WOS] | singlet oxygen ; nucleophilic substitutions ; gas-phase ; density ; phosphorus ; mechanism ; olefins |
收录类别 | SCI |
语种 | 英语 |
WOS记录号 | WOS:000277870600013 |
公开日期 | 2015-11-17 |
内容类型 | 期刊论文 |
源URL | [http://159.226.238.44/handle/321008/141750] |
专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
作者单位 | 1.Shandong Normal Univ, Coll Chem Chem Engn & Mat Sci, Jinan 250014, Peoples R China 2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China |
推荐引用方式 GB/T 7714 | Liu, Jianbiao,Chen, Dezhan,Zhang, Guiqiu,et al. On the origin of decomposition of triphenyl phosphite ozonide accelerated by ammonia or pyridine water solution[J]. journal of molecular structure-theochem,2010,948(1-3):71-77. |
APA | Liu, Jianbiao.,Chen, Dezhan.,Zhang, Guiqiu.,Zhang, Yuhua.,Zhang, Honghong.,...&Shen, Guanlin.(2010).On the origin of decomposition of triphenyl phosphite ozonide accelerated by ammonia or pyridine water solution.journal of molecular structure-theochem,948(1-3),71-77. |
MLA | Liu, Jianbiao,et al."On the origin of decomposition of triphenyl phosphite ozonide accelerated by ammonia or pyridine water solution".journal of molecular structure-theochem 948.1-3(2010):71-77. |
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