The study of detection for transient silicon compuneds using a Fourier transform microwave spectrometer

傅里叶变换微波谱仪检测瞬态硅化合物的研究

• 批准号: 12640505
• 负责人: KAWASHIMA Yoshiyuki
• 金额: $ 2.24万
• 依托单位: Kanagawa Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640505/
• 关键词: rotational spectra; FT microwave spectroscopy; silicon compound; hyperfine structure; substituted structure; internal rotation; puckering motion

In order to investigate shote lived dimethylsilane which plays important role in organosilicon reactions, we tried to detect dimethylsilane in the pyrolysis and discharge reactions of dimethylchlorosilane and trimethylenedimethylsilane. It has not been observed by means of a Fourier transform microwave spectrometer, however, many rotational transitions of the parent species were observed. Therefore the molecular structures and vibrational motions of DMC1Si and TMDMSi were studied. In the addition, the 101-000 transition of a short lived molecule, Si2H2, was detected during a discharge reaction of silane.The microwave spectra of five isotopic species of chlorodimethylsilane have been investigated in the region 5 to 20 GHz using a Fourier transform microwave spectrometer. The molecular structure of (CH_3)_2SiHCl obtained by the substitution method is the following one: r_s(Si-Cl) = 2.0604 (10) A^^°, r_s (Si-C) = 1.8542 (10) A^^°, /ClSiC = 108.43 (20)°, and /CSiC = 112.32 (15)°. The quadrupole coupling constants of the chlorine atom was obtained and yielded x_<zz> = -35.556 (6) MHz and 65 % as an ionic character of the chlorine atom. The estimated value of the potential barrier V_3 of internal rotation of two methyl tops is in agreement with those of the related molecules.The a-type transitions of isotopic species, normal, ^<29>Si, ^<30>Si, and ^<13>C, of 1, 1-dimethylsilacyclobutane were observed and assigned. Each transition except ^<13>C species in the methyl group has six components because of the splittings due to the internal rotation of two methyl tops and the ring puckering. The observed spectra of two ^<13>C species in the methyl group were much complicated and distinguished from the spectra of two ^<13>C species in the ring. The estimated value of the potential barrier V_3 of internal rotation of two methyl tops is in agreement with those of the related molecules.

为了研究在有机硅反应中起重要作用的二甲基硅烷，我们尝试在二甲基氯硅烷和三亚甲基二甲基硅烷的热解和放电反应中检测二甲基硅烷。用傅里叶变换微波光谱仪没有观察到这一现象，但观察到了母体物种的许多转动跃迁。因此，我们对DMC1Si和TMDMSi的分子结构和振动进行了研究。此外，在硅烷放电反应中检测到了短寿命分子Si2H2的101-000跃迁。用傅里叶变换微波光谱仪研究了5-20 GHz范围内五种氯代二甲基硅烷的微波光谱。由取代法得到的(CH_3)_2SiHCl的分子结构如下：r_S(Si-Cl)=2.0604(10)A^°，r_S(Si-C)=1.8542(10)A^°，/ClSiC=108.43(20)°，/CsIC=112.32(15)°。得到了氯原子的四极耦合常数，得到了氯原子的离子特性为x_&lt；zz&gt；=-35.556(6)MHz和65%。1，1-二甲基硅环丁烷的两个甲基顶的内旋势垒V_3的估计值与相关分子的势垒V_3是一致的。由于两个甲基顶端的内部旋转和环状折叠造成的分裂，除了甲基团中的13个C物种外，每个转变都有6个组分。观察到的甲基中两个物种的光谱非常复杂，与环中两个物种的光谱有所不同。两个甲基顶的内旋势垒V_3的估计值与相关分子的估计值一致。

项目成果

Kawashima,Yoshiyuki: "The rotational spectrum of chlorodimethylsilane using Fourier microwave spectroscopy"Journal of Molecular Structure. Vol. 563-563. 227-230 (2001)

Kawashima，Yoshiyuki：“使用傅立叶微波光谱法分析二甲基氯硅烷的旋转光谱”分子结构杂志。

Yoshiyuki Kawashima: "The rotational spectrum of chlorodimethylsilane using Fourier transform microwave spectroscopy"Journal of Molecular Structure. (2001)

Yoshiyuki Kawashima：“使用傅里叶变换微波光谱法分析二甲基氯硅烷的旋转光谱”分子结构杂志。

Yoshiyuki Kawashima: "The rotational spectrum of chlorodimethylsilane using Fourier transform microwave spectroscopy"Journal of Moleculaar Structure. 563-564. 227-230 (2001)

Yoshiyuki Kawashima：“使用傅立叶变换微波光谱的二甲基氯硅烷的旋转光谱”分子结构杂志。

Yoshiyuki Kawashima: "The rotational spectrum of chlorodimethylsilane using Fourier transform microwave spectroscopy"Journal of Molecular Structure. 563-564. 227-230 (2001)

Yoshiyuki Kawashima：“使用傅里叶变换微波光谱法分析二甲基氯硅烷的旋转光谱”分子结构杂志。