Sequential Photoinduced Reaction of Reactant Pairs in Extremely Low Temperature

极低温下反应物对的顺序光致反应

• 批准号: 06453018
• 负责人: SHIBUYA Kazuhiko
• 金额: $ 4.54万
• 依托单位: TOKYO INSTITUTE OF TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06453018/
• 关键词: photoreaction; nitrogen dioxide; amine; propene; bimolecular reaction; intermolecular atom transfer; infrared spectroscopy; reaction intermediate; 極低温固体; ジエン

Visible light induced oxygen atom transfer from NO_2 to propene has been investigated in low-temperature argon and xenon matrices. The reaction intermediate was propyl nitrite radical and the final products were methyl oxirane and NO.Conformational structure of propyl nitrite radical was determined by the vibrational analysis of N=O and N-O stretching modes for the normal and ^<18>O-isotope-substituted species. From the analysis of absorbance growth behaviors of the infrared bands for propyl nitrite radical and methyl oxirane, first-order rate constants were determined by least squares fittings. The photoreaction of propane and NO_2 in xenon matrices was found to occur more rapidly than in argon matrices. The wavelength dependence of the rate constants is also discussed.The visible light-induced reaction of NO_2 with methlamine in a cryogenic argon matrices has also been investigated using an FTIR spectrometer. The photochemical products were identified as methyleneimine, water and nitric oxide. This photoinduced dehydrogenation reaction is interpreted by the following reaction sequence : (1) photoexcitation of NO_2, (2) oxygen atom tranfer from excited NO_2 to methylamine and (3) isomerization from the methylamine N-oxide to methylhydroxylamine, followed by (4) dissociation into methyleneimine and water. It was confirmed by the infrared spectrum that two of the dissociation products interact with each other in the matrix cage.

研究了低温氩气和氙气基质中可见光诱导氧原子从NO_2向丙烯的转移。反应中间体为亚硝酸盐丙基，最终产物为氧环甲烷和NO。通过对正常和^<18>O同位素取代种的N=O和N-O伸展模式的振动分析，确定了亚硝酸盐丙基的构象结构。通过对亚硝酸盐丙基和氧环甲酯红外光谱吸光度增长行为的分析，用最小二乘拟合确定了一阶速率常数。结果表明，丙烷和NO_2在氙基质中的光化学反应比在氩基质中的反应更快。本文还讨论了速率常数与波长的关系。用FTIR光谱仪研究了低温氩气基质中NO_2与甲胺的可见光诱导反应。光化学产物经鉴定为亚甲亚胺、水和一氧化氮。光诱导脱氢反应的反应顺序为：(1)NO_2光激发，(2)氧原子从激发的NO_2转移到甲胺，(3)甲胺n -氧化物异构化成甲基羟胺，(4)解离成亚胺和水。红外光谱证实了两种解离产物在基质笼中相互作用。

项目成果

Nobuaki Tanaka: "Visible Light Induced Oxygen Afom Transfer from NO_2 to (CH_3)_2NH in a Cryogenic Ar matrix" Jourmal of Physical Chemistry. 100(4月号揚載予定). (1996)

Nobuaki Tanaka：“低温 Ar 基质中的可见光诱导氧原子转移 (Visible Light Induced Oxygen Afom Transfer from NO_2 to (CH_3)_2NH)”Journal of Physical Chemistry 100（计划于 4 月出版）。

N.Tanaka, j.Oike, K.Shibuya, and M.Nakata: "Visible Light Induced Oxygen Atom Transfer form NO_2 to (CH_3)_2NH in a Cryogenic Ar Matrix" J.Phys.Chem.100, (April issue, 1996).

N.Tanaka、j.Oike、K.Shibuya 和 M.Nakata：“可见光诱导氧原子在低温 Ar 基质中从 NO_2 转移到 (CH_3)_2NH”J.Phys.Chem.100，（1996 年 4 月号）

Nobuaki Tanaka: "Visible Light Induced Oxygen Atom Transfer from NO_2 to (CH_3)_2 NH in a Cryogenic Ar Matrix" Journal of Physical Chemistry. 100(4月号掲載予定). (1996)

Nobuaki Tanaka：“可见光诱导氧原子在低温 Ar 基质中从 NO_2 转移到 (CH_3)_2 NH”，《物理化学杂志》100（计划于 1996 年 4 月出版）。

Mari Akiike: "vander Waals vibrations of NO-CH_4 complexes in the A^2Σ^+ state" Chemical Physics Letters. 243. 89-93 (1995)

Mari Akiike：“A^2Σ^+ 状态下 NO-CH_4 配合物的范德华振动”《化学物理快报》243. 89-93 (1995)。

Nobuaki Tanaka: "Photoinduced dehydrogenation reation of CH_3NH_2 by NO_2 in a cryogenic Ar matrix. Identification of the CH_2=NH・・・H_2O complex" Chemical Physics Letters. 232. 109-114 (1995)

Nobuaki Tanaka：“低温 Ar 基质中 NO_2 引起的 CH_3NH_2 的光诱导脱氢反应。CH_2=NH...H_2O 复合物的鉴定”《化学物理快报》232. 109-114 (1995)。