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TIME-RESOLVED IR SPECTROMETRIC DETECTION SYSTEM FOR KINETIC AND STRUCTURAL STUDIES OF REACTIVE INTERMEDIATES AT AMBIENT TEMPERATURE

用于反应中间体在环境温度下的动力学和结构研究的时间分辨红外光谱检测系统

基本信息

批准号：
11554031
负责人：
TAKAHASHI Yasutake
金额：
$ 8.9万
依托单位：
MIE UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

The goal of this study is to build a time-resolved IR detection system for laser flash photolysis (LFP). It is designed to be compact and suited for kinetic and structural studies of gain high cost-performance. The operational software for our LFP system is also modified so that it can be synchronized with the IR detection system. So far, intermediates with sufficient extinction coefficients and the lifetime of some hundred seconds can be readily detected.On the other hand, time-resolved spectroscopic studies of reactive intermediates are also carried out with UV-VIS detection. We are interested in this particular carbene and have attempted to generate benzocyclobutenylidene from precursors in order to investigate its reactivity. LFP (XeCl, 308 nm) of N-(2-phenylazyridyl)imine of benzocyclobutenone results in transient species with its absorption maximum around 450 nm. After these transients disappeared with the lifetime of 1 μs, a longer-lived species was observed as a weak absorption at 510 nm with the lifetime of 660 μs. We assign the former transient as being due to benzocyclobutenylidene based on the observed reactivity toward alkenes and alcohols. The latter 510 nm transient can be assigned as diazobenzocyclobutene because this species can be quenched by dipolarophiles such as fumaronitrile.Similar LFP of the same precursor with IR detection allowed us to observe absorption at 2042 cm^<-1>, which can be assigned as being due to diazobenzocyclobutene. The lifetime is 1 ms, which is in good agreement with the observation by UV-VIS detection. Further progress in the instrumental sensitivity and time-resolution is underway so that benzocyclobutenylidene and the pyridine ylide can be observed.

本研究的目的是建立一个时间分辨的激光闪光光解（LFP）红外探测系统。它设计紧凑，适合动力学和结构研究，以获得高性价比。我们的LFP系统的操作软件也进行了修改，使其能够与红外探测系统同步。到目前为止，具有足够消光系数和数百秒寿命的中间体可以很容易地检测到。另一方面，活性中间体的时间分辨光谱研究也可以用UV-VIS检测进行。我们对这种特殊的卡宾很感兴趣，并试图从前体中生成苯并环丁烯叉，以研究其反应性。苯并环丁烯酮的N-（2-苯基氮杂吡啶基）亚胺的LFP（XeCl，308 nm）产生瞬态物质，其吸收最大值约为450 nm。在这些瞬态以1 μs的寿命消失之后，观察到更长寿命的物种，其为在510 nm处的弱吸收，寿命为660 μs。我们分配前瞬态是由于苯并环丁烯亚基的基础上观察到的反应性对烯烃和醇。后一个510 nm的瞬变可以归属为重氮苯并环丁烯，因为这种物质可以被亲偶极试剂如乙腈淬灭。用IR检测的相同前体的类似LFP允许我们观察到在2042 cm-1处的吸收，<-1>其可以归属为由于重氮苯并环丁烯。寿命为1 ms，这与UV-VIS检测的观察结果很好地一致。仪器灵敏度和时间分辨率的进一步进展正在进行中，以便可以观察到苯并环丁烯叉和吡啶叶立德。