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Development of Novel Reactions in Cluster-Mediated Anion Chemistry

簇介导阴离子化学新反应的发展

基本信息

批准号：
15350006
负责人：
NAGATA Takashi
金额：
$ 6.98万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2005
项目状态：
已结题

项目摘要

The aim of this research project was the development of novel gas-phase reactions, which can be categorized as "cluster-mediated" anion chemistry, by exploiting unique properties of molecular cluster anions, such as floppiness of their structures, affinity for an excess electron and propensity for molecular uptake. The results are summarized as follows:1.The anion radical of carbon dioxide, CO_2^<・->, sustained on a surface of gas-phase (H_2O)_n was found to behave as a carboxylation reagent for alkyl halides (RX), presenting a sharp contrast to the reactions of CO_2^<・->in solutions, where the interaction of CO_2^<・->with RX leads to the formation of X-through dissociative electron transfer. The (H_2O)_n,"microflask" acts not only as a sustainer of the unstable CO_2^<・->reagent but also as a stabilizer of the product anions.2.Radical addition reactions of CO_2^<・->against NO, O_2 and conjugated alkenes were observed in the (CO_2)_n^- microflask. Those reactions in (CO_2)_n^- are to be categorized as a one-step carboxylation process by the reductive activation of CO_2 within the microflask.3.The geometrical and electronic properties of [(CO_2)_n(H_2O)_m]^- as a microflask of binary components were investigated by ab initio calculations at the MP2/6-311++G(d, p) level. The number of isomeric forms determined for n = 1-4 and m = 1, 2 amounts to 117 in total, providing information on the stabilization mechanism for [(CO_2)_n(H_2O)_m]^-.4.The selective stabilization of CO_2^<・-> by entrainer molecules in [(CO_2)_n(H_2O)_m]^- with n 【greater than or equal】4 was revealed by the measurement of infrared photodissociation spectra of [(CO_2)_n(H_2O)_m]^- in the 2800-3800 cm^<-1> region.5.Photodissociation of the gas-phase triiodide anion and its complexes, I_3^- and I_3^-(H_2O)_m, was investigated using photofragment TOF mass spectrometry, which leads to the detailed understanding of the nonadiabatic dissociation dynamics and the solvent effects on the product branching.

本研究项目的目的是开发新型气相反应，可归类为“簇介导”阴离子化学，通过利用分子簇阴离子的独特性质，如其结构的软性，对多余电子的亲和力和分子吸收的倾向。研究结果总结如下：1。二氧化碳的阴离子自由基CO_2^<··->在气相（H_2O）_n表面表现为烷基卤化物（RX）的羧基化试剂，这与CO_2^<··->在溶液中的反应形成鲜明对比，CO_2^<··->与RX相互作用，通过解离电子转移形成x。（h2o） n“微烧瓶”不仅作为不稳定的CO_2^<·->试剂的维持剂，而且作为产物阴离子的稳定剂。在（CO_2）_n^-微烧瓶中，观察了CO_2^<·->对NO、O_2和共轭烯烃的自由基加成反应。在（CO_2）_n^-中的反应可归类为在微瓶内通过CO_2的还原活化而进行的一步羧基化过程。在MP2/6-311++G（d, p）水平上，用从头计算方法研究了[(CO_2)_n(H_2O)_m]^-作为二元组分微烧瓶的几何和电子性质。n = 1-4和m = 1,2的同分异构体总数达117种，为[(CO_2)_n(H_2O)_m]^- 4的稳定机理提供了信息。通过对[(CO_2)_n(H_2O)_m]^-在2800 ~ 3800 cm^<-1>范围内的红外光解光谱的测量，揭示了携带剂分子在n【大于或等于】4时对[(CO_2)_n(H_2O)_m]^- CO_2^<··>的选择性稳定作用。采用光碎片TOF质谱法研究了气相三碘阴离子及其配合物I_3^-和I_3^-(H_2O)_m的光解作用，从而详细了解了非绝热离解动力学和溶剂对产物分支的影响。