The Effect of Si d-Orbital in the Ion/Molecule Reactions of Organosilicon

Si d轨道对有机硅离子/分子反应的影响

基本信息

批准号：
09650961
负责人：
TAKEUCHI Takae
金额：
$ 2.3万
依托单位：
Nara Women's University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

The purpose of this study is to provide evidence for a facile rearrangement of organosilicon cations and anions and to clarify the mechanisms and the effective factors in the specific reactions which are not observed in organic compounds without metallic atoms.1. Ion/molecule reactions of silene cation radicals with alkene molecules were investigated using FTICR mass spectrometry. The silene cation radicals [(CH_3)_2SiCH_2]^+ and [(CD_3)_2SiCH_2]+ were generated by 70 eV-electron ionization of 1-dimethyl-1-silacyclobutane and l, 1-[D_6]dimethyl-1-silacyclobutane. After these silene cation radicals were isolated in the FTICR cell, they were allowed to react with ethene, [_4]ethene, or propene molecules under ultra-high-vacuum conditions (l0^<-8>-l0^<-9> mbar). The resulting FTICR spectra show that the adduct ions, produced in the ion/molecule reactions, should have a four-membered ring structure.2. In order to make an SiC multiple bond, an electron-impact ionization (EI), a chemical ionization (CI) and a fast-ion-bombardment ionization of 2-adamantyl-4-tert-butyl-2-trimethylsiloxy- 1,1-bis(trimethylsilyl)- l-silacyclobut-3-ene were examined in order to generate ions containing an SiC double or triple bond using both a Bruker Apex^<TM+> 47e FT-ICR mass spectrometer and a JEOL JMS SX/SX 1 02A four-sector tandem mass spectrometer. From the results of high-resolution mass measurement, the elementary composition of fragment ions at m/z 330 was found to be C_<20>H_<34>Si_2^+. The results of MS/MS/MS and ab initio MO calculations showed that the structure of the m/z 330 ion is a four-membered ring containing an Si=C double bond.

这项研究的目的是为有机硅阳离子和阴离子的轻松重排提供证据，并阐明在没有金属原子的有机化合物中未观察到的特定反应的机理和有效因素。1。使用FTICR质谱法研究了锡烯阳离子自由基与烯烃分子的离子/分子反应。锡烯阳离子自由基[（CH_3）_2SICH_2]^+和[（CD_3）_2SICH_2]+是由1-二甲基-1-二甲基丁烷和L，1- [d_6] dimethyl-1-二酰基甲烷的1-二甲基-1-硅烷基丁烷和L，1-二甲基-1-二甲基丁烷和L，生成的。在将这些锡烯阳离子自由基分离在FTICR细胞中后，它们被允许在超高vacuum条件下与乙烯，[_4]乙烯或丙烯分子反应（L0^<-8> -l0^<-9> mbar）。所得的FTICR光谱表明，在离子/分子反应中产生的加合离子应具有四元环结构。2。为了建立SIC多键，电子冲击电离（EI），化学离子化（CI）和2-腺苷-4-tert-4-TERT-2-叔丁基-2-二甲基硅氧基-1,1-1-1-偶联的（三甲基甲基甲基甲基甲基甲基甲基）的快速离子炸弹电离（三甲基甲基甲基） - 丝状甲基二 - 三甲基均应均可用来排序，以排序为固定剂，以排序为排序。 Bruker Apex^<tm+> 47E FT-ICR质谱仪和JEOL JMS SX/SX 1 02A四个扇区串联质谱仪。从高分辨率质量测量的结果中，发现M/z 330处片段离子的基本组成为C_ <20> H__ <34> SI_2^+。 MS/MS/MS和AB INTIOM计算的结果表明，M/z 330离子的结构是一个四元环，其中包含SI = C双键。