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特性，例如其结构的磷，对过量电子和分子吸收的可靠性，可以将新型气相反应的发展开发为“簇介导的”阴离子化学。结果总结如下：1。在气相（H_2O）_n表面维持的二氧化碳的阴离子co_2^<・->持续的阴离子被认为是烷基卤化物（rx）的羧基化试剂（rx）的羧基化试剂，与co_2^<・ <・ <・ <・ <・ <・ <・ <・ <・ <导致形成X型解离电子传递。（h_2o）_n，“微屏幕”不仅可以作为不稳定的CO_2^<・->试剂的维持者，而且还可以作为产品阴离子的稳定剂。2.CO_2^<・>对NO，O_2和CONNECT的RADICal添加反应在（co_2）_n^-n^-microf.lask中。（co_2）_n^中的这些反应应通过降低微屏幕中的co_2的激活来归类为一步羧化过程。3。[（co_2）_n（h_2o）_m] _n（h_2o）_m]^ - 的几何和电子属性和电子属性的二进制组合++++++yers y+ers 3+ersii+ers 3+ersii+ersii+ers 3++ p）水平。确定n = 1-4和m = 1的异构形式的数量总计117总计117，提供了有关[（co_2）_n（h_2o）_m] _m]^ - 。的稳定机制的信息。4。co_2^<・->的选择性稳定，由较大的go_2^<・>> in（co_2）n（co_2）n（co_2）^n（h_2）通过测量[（co_2）_n（h_2o）_m]^ - 在2800-3800 cm^<-1>区域中的红外光解离光谱。光谱法会导致对非绝热解离动力学和溶剂对产品分支的影响的详细理解。