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.

该研究项目的目的是通过利用分子簇阴离子的独特性质（例如其结构的松散性、对多余电子的亲和力）开发新型气相反应，该反应可归类为“簇介导”阴离子化学研究结果概括如下： 1.气相(H_2O)_n表面存在的二氧化碳阴离子自由基CO_2^<·->表现为阴离子自由基。卤代烷（RX）的羧化试剂，与溶液中CO_2^<·->的反应形成鲜明对比，其中CO_2^<·->与RX相互作用，通过解离电子转移形成X-。 (H_2O)_n，“微瓶”不仅充当不稳定的CO_2^<·->试剂的维持剂，而且充当产物阴离子的稳定剂。2.自由基加成反应在(CO_2)_n^-微瓶中观察到CO_2^<·->针对NO、O_2和共轭烯烃的反应，(CO_2)_n^-中的这些反应被归类为还原活化的一步羧化过程。 3.[(CO_2)_n(H_2O)_m]^-作为二元组分的微烧瓶的几何和电子性质通过在 MP2/6-311++G(d, p) 水平上从头算来研究 n = 1-4 和 m = 1, 2 的异构体形式总数为 117，提供了有关该异构体的确定信息。 [(CO_2)_n(H_2O)_m]^-.4.夹带剂分子对CO_2^<・->的选择性稳定通过测量[(CO_2)_n(H_2O)_m]^-在2800-3800 cm^的红外光解光谱，揭示了[(CO_2)_n(H_2O)_m]^-，其中n【大于或等于】4 <-1>区域.5.气相三碘化物阴离子及其配合物的光解离，I_3^-和使用光碎片TOF质谱法研究了I_3^-(H_2O)_m，从而详细了解非绝热解离动力学和溶剂对产物支化的影响。