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

在本研究中，我的目标是开发光谱仪器，可以直接和选择性地检测化学键非常弱的化学物种，以了解涉及过渡金属中心的反应机理。今年，继去年的工作（主要是设计和建造的装置），我考虑了该装置的应用的可能性，通过测量过渡金属化合物的飞行时间光谱的过渡金属化学的化学键较弱的一些改进和性能测试的装置。1.（宽波长真空紫外激光的产生）通过以氪气为非线性介质的双光子共振四波差频，我已经能够得到宽波长范围（120-180 nm）的线可调谐真空紫外激光光源（线宽0.4 cm-2<-1>）。2.（仪器性能测试）以苯C_6H_6为工作分子，对该飞行时间质谱仪进行了性能测试 ...更多信息 S光谱仪进行了改进。我已经证明，它具有约150 amu的分辨率，这几乎等于理论值，并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）在苯的电离势（134.1nm）附近进行单光子电离，得到了一个只有C_6H_6^+母离子而没有其它离子碎片的飞行时间谱。4.（过渡金属羰基单光子电离光谱的测量）通过Cr（CO）_6在146 nm（8.49 eV）处的单光子电离，我可以观察到TOF光谱（I. P.= 8.4eV），只有Cr（CO）_6^+的母离子峰。我的实验结果表明，即使是化学键较弱的化学物种，也有可能在没有任何碎裂的情况下测量飞行时间质谱。本研究所开发的实验装置对涉及许多弱化学相互作用的过渡金属化学具有很强的应用价值。少

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