Reaction of Coordinatively Unsaturated Transition Metal Carbonyl with Small Molecules ; Highly Sensitive Detection of Reaction Products with Vacuum Ultra Violet Laser Photo-Ionization Mass Spectrometer

配位不饱和过渡金属羰基与小分子的反应；

• 批准号: 09640603
• 负责人: ISHIKAWA Yo-ichi
• 金额: $ 0.32万
• 依托单位: Kyoto Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640603/
• 关键词: Vacuum Ultra Violet Laser Light; One Photon Ionization; Time-of-Flight Mass Spectrometer; Transition Metal Species; Two Photon Resonance Four-Wave Mixing; Ionization Threshold Spectroscopy; 共鳴四波混合; 非共鳴逓倍法

In this research, I have aimed the development of spectroscopic apparatus which can detect directly and selectively chemical species with very week chemical bonds in order to understand reaction mechanism involving transition metal centers. This year, following the last year works (mainly design and construction of the apparatus), I have considered the possibility of an application of this apparatus to transition metal chemistry with week chemical bonds by measuring time-of-flight spectra of transition metal compounds after some improvement and performance test of the apparatus. 1. (Production of wide wavelength VUV laser light) By means of two-photon resonance four wave difference frequency mixing with Kr gas as non-linear medium, I have been able to get a wide wavelength range (120-180 nm) line tunable VUV laser light source (line width 0.4 cm^<-1>). 2. (Performance test of the apparatus) With use of Benzene C_6H_6 as working molecule, I have checked the specification of this TOF-MAS … More S spectrometer and performed some improvements. I have certified that it has a resolution of about 150 amu which is almost equal to a theoretical value and also that the spectral line width is restricted mainly by the energy resolution. 3. (Measurement of C_6H_6 one-photon ionization spectrum) By means of one-photon ionization around at the ionization potential (134.1 nm) of Benzene, a TOF spectrum with only parent ion of C_6H_6^+ without any other ion fragment could be observed. 4. (Measurement of transition metal carbonyl one-photon ionization spectrum) I could have observed a TOF spectrum by an one-photon ionization at 146 nm (8.49 eV) of Cr(CO)_6 (I.P.=8.4eV) in which only a parent ion peak of Cr(CO)_6^+ did exist. My experimental results have suggested that it is possible to measure TOF-MASS spectrum without any fragmentation even for chemical species with week chemical bond. The experimental apparatus developed in this study can be though to be very powerful for transition metal chemistry involving many week chemical interactions. Less

在这项研究中，我的目标是开发一种可以直接和选择性地检测具有极小化学键的化学物质的光谱装置，以了解涉及过渡金属中心的反应机理。今年，继去年的工作（主要是设备的设计和建造）之后，我考虑了通过对设备进行一些改进和性能测试，通过测量过渡金属化合物的飞行时间光谱，将该设备应用于具有周化学键的过渡金属化学的可能性。1. （宽波长VUV激光光源的生产）通过双光子共振四波差频混合，以Kr气体为非线性介质，我已经能够得到宽波长范围（120-180 nm）线可调谐的VUV激光光源（线宽0.4 cm^<-1>）。2. （仪器性能测试）以苯C_6H_6为工作分子，对该TOF-MAS…More S光谱仪的性能进行了检查，并进行了改进。我已经证实它的分辨率约为150 μ m，几乎等于理论值，而且谱线宽度主要受能量分辨率的限制。3. （C_6H_6单光子电离光谱的测量）通过在苯的电离势（134.1 nm）附近的单光子电离，可以观察到只有C_6H_6^+的母离子而没有其他离子碎片的TOF光谱。4. （过渡金属羰基单光子电离光谱的测量）我可以通过在146 nm （8.49 eV）处对Cr(CO)_6 （I.P.=8.4eV）进行单光子电离观察到TOF光谱，其中只有Cr(CO)_6^+的母离子峰存在。我的实验结果表明，即使对化学键较弱的化学物质，也可以在不破碎的情况下测量tof -质谱。在本研究中开发的实验装置可以被认为是非常强大的过渡金属化学涉及许多周的化学相互作用。少

项目成果

Tomothiro WAKABAYASHI: "Absolute Rate Constants of Mo_2 (X^1SIGMA-_g^+) and Mo (a^7S_3) with NO at Room Temperature" Chem Lett.331-332 (1997)

Tomothiro WAKABAYASHI：“室温下 Mo_2 (X^1SIGMA-_g^ ) 和 Mo (a^7S_3) 与 NO 的绝对速率常数” Chem Lett.331-332 (1997)

Yoshihiro NAKAI: "Neutral Molybdenum Atom and Dimer Formations in Laser Induced Plasma:Emission Study of 355-nm Pulse Laser Photolysis of Mo(CO)_6 in the Gas Phase" Appl.Phys.B.66. 621-631 (1998)

Yoshihiro NAKAI：“激光诱导等离子体中的中性钼原子和二聚体形成：气相中 Mo(CO)_6 的 355 nm 脉冲激光光解的发射研究”Appl.Phys.B.66。

Tomohiro WAKABAYASHI: "Absolute Rate Constants of Mo_2(X^1Σ_g^+)and Mo(a^7S_3)with NO at Room Temperature" Chem Lett.331-332 (1997)

Tomohiro WAKABAYASHI：“室温下 Mo_2(X^1Σ_g^+) 和 Mo(a^7S_3) 与 NO 的绝对速率常数” Chem Lett.331-332 (1997)

Tomohiro WAKABAYASHI: "Absolute Rate Constants of Mo_2(X^1Σ^+_g)and Mo(a^7S_3)with NO at Room Temperature" Chem Lett.331-332 (1997)

Tomohiro WAKABAYASHI：“室温下 Mo_2(X^1Σ^+_g) 和 Mo(a^7S_3) 与 NO 的绝对速率常数” Chem Lett.331-332 (1997)

Yoshihiro NAKAI: "Neutral Molybdenum Atom and Dimer Formations in Laser Induced Plasma : Emission Study of 355-nm Pulse Laser Photolysis of Mo(CO)_6 in the Gas Phase" Appl.Phys.B. 66. 621-631 (1998)

Yoshihiro NAKAI：“激光诱导等离子体中的中性钼原子和二聚体形成：气相中 Mo(CO)_6 的 355 nm 脉冲激光光解的发射研究”Appl.Phys.B。