1998 Fiscal Year Final Research Report Summary
The Effect of Si d-Orbital in the Ion/Molecule Reactions of Organosilicon
| Project/Area Number |
09650961
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Nara Women's University |
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Principal Investigator |
TAKEUCHI Takae Nara Women's University, Faculty of Science, Research Associate, 理学部, 助手 (80201606)
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| Co-Investigator(Kenkyū-buntansha) |
YAMAMOTO Masao Nara Women's University, Faculty of Science, Professor, 理学部, 教授 (80028159)
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| Project Period (FY) |
1997 – 1998
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| Keywords | Fourier Transform Ion Cyclotron Resonance / disilyne / Silacyclobutadiene / Silacyclobutene / MS / MS / ab initio MO / Ion / Molecule Reaction / Collisionally Activated Decomposition |
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| Research Abstract |
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.
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