silyl-d3 radical | 69103-84-0

• 英文名称: silyl-d3 radical
• 英文别名: silyl radical；silyl-d3；SiD3
• CAS: 69103-84-0
• 化学式: H₃Si
• 分子量: 34.0855
• InChiKey: OLRJXMHANKMLTD-FIBGUPNXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.18
• 重原子数：
  1
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  silyl-d3 radical 、 氧化亚氮 以 gaseous matrix 为溶剂， 生成
  参考文献：
  名称：

  Kinetics and Thermochemistry of SiH₃ + NO and SiD₃ + NO Reactions:  Pressure Falloff and SiH₃−NO Bond Energy

  摘要：

  The reactions of silyl and silyl-d(3) radicals with nitric oxide, SiH3 + NO --> SiH3NO (1) and SiD3 + NO --> SiD3NO (2), have been studied using pulsed excimer laser photolysis coupled with time-resolved photoionization mass spectrometry over the temperature range 301-817 K. The rate constants were measured in the ranges 0.75 x 10(16) less than or equal to [He] less than or equal to 32.0 x 10(16) molecules cm(-3) and 301 less than or equal to T less than or equal to 611 K. Both reactions are in the pressure falloff regions considerably far from the true low-pressure limit. RRKM fittings using the Tree factorization approach yielded the low-pressure limit and high-pressure limit rate constants: (1,tri) = (3.12 +/- 0.12) x 10(-29)(T/298)(-2.96+/-0.09) cm(6) molecule(-2) s(-1), k(2,tri) = (9.02 +/- 0.40) x 10(-29)(T/298)(-3.36+/-0.11) cm(6) molecule(-2) s(-1), k(1,inf) = (3.9 +/- 1.1) x 10(-11)(T/298)(-1) cm(3) molecule(-1) s(-1), and k(2,inf) = (5.0 +/- 1.3) x 10(-11)(T/298)(-1) cm(3) molecule(-1) s(-1). Equilibrium constants were measured in the temperature range 711-817 K. The standard enthalpies of reactions 1 and 2 were determined using the third law method. The bond energies determined are DH0 degrees(H3Si-NO) = 153.7 +/- 5.7 kJ mol(-1), DH(298)degrees(H3Si-NO) = 158.9 +/- 5.7 kJ mol(-1), DH0 degrees(D3Si-NO) = 156.1 +/- 5.7 kJ mol(-1), and DH(298)degrees(D3Si-NO) = 160.8 +/- 5.7 kJ mol(-1). This value of DH0 degrees(H3Si-NO) is ca. 30 kJ mol(-1) higher than previous estimates. Ab initio structural parameters were used to calculate the thermodynamic functions of SiH3, SiD3, SiH3NO, and SiD3NO. Both the singlet and the low-lying triplet states were taken into account for the adduct molecules. The calculated thermodynamic functions were used to obtain the standard entropies of the reactions 1 and 2: Delta S(298)degrees(rxn 1) = 143.1 J mol(-1) K-1 and Delta S(298)degrees(nm 2) = 146.0 J mol(-1) K-1. The rate constants of the reaction SiH3NO + NO --> products (3) were measured in the temperature range 301-611 K: k(3) = (2.95 +/- 0.38) x 10(-13)(T/298)(-1.59+/-0.29) cm(3) molecule(-1) s(-1).

  DOI：

  10.1021/jp970288n
• 作为产物：
  描述：

  硅烷 在 Cl₂ 作用下， 生成 silyl-d3 radical
  参考文献：
  名称：

  Multiphoton ionization of SiH₃ and SiD₃ radicals: Electronic spectra, vibrational analyses of the ground and Rydberg states, and ionization potentials

  摘要：

  The electronic spectra of silyl radicals, SiH3 and SiD3, were observed between 310 and 430 nm (46 000–64 000 cm−1) by resonance enhanced multiphoton ionization (REMPI) mass spectroscopy. The spectra were generated through a 2+1 REMPI mechanism. Two Rydberg series originating from planar, D3h point group states were observed. One series, of quantum defect δ=1.45(2), is comprised of the Ẽ 2A″2 (4p), J̃ 2A″2(5p), and M̃ 2A″2(6p) Rydberg states which have origins at ν0–0 =48 438, 56 929, and 60 341 cm−1 in SiH3 and at ν0–0 =48 391, 56 874, and 60 267 cm−1 in SiD3. In SiD3 the P̃ 2A″2(7p) Rydberg origin was observed at ν0–0 =62 002 cm−1. The H̃, K̃, and Ñ states observed in the SiD3 spectrum comprise the second Rydberg series, δ=2.09, and were tentatively assigned as ns 2A′1 Rydberg states (n=5, 6, 7). The K̃ and Ñ origins were observed at ν0–0 =58 417 and 61 005 cm−1. A fit of the Rydberg formula to the np 2A″2(n≥5) origins found the adiabatic ionization potential of the SiH3 and SiD3 radicals to be IPa=8.135(+5,−2) eV and IPa=8.128(1) eV, respectively. Detailed vibrational analyses of these Rydberg states are presented. Analysis showed that in the Ẽ 2A″2 (4p) state of the SiH3 radical ω2 (a″2 symmetric bend)=796(7) and 2ω4 /2(e′ degenerate bend)=870(5) cm−1 and that in SiD3 radical ω′1 (a1 SiH3 symmetric stretch)=1576(3), ω′2 =589(3), and 2ω4 /2=635(6) cm−1. The REMPI spectra exhibited ν″2 hot bands from vibrational levels as high as Ev =2073 cm−1 in the X̃ 2A1state. Modeling calculations, which fit the numerous ν″2 hot bands, predicted barriers to inversion of Binv =1935 cm−1 and Binv =1925 cm−1 for SiH3 and SiD3 X̃ 2A1 radicals, respectively.

  DOI：

  10.1063/1.456909

文献信息

• Infrared Spectra of Group 14 Hydrides in Solid Hydrogen:  Experimental Observation of PbH₄, Pb₂H₂, and Pb₂H₄
  作者：Xuefeng Wang、Lester Andrews

  DOI：10.1021/ja029862l

  日期：2003.5.1

  and Pb atoms have been co-deposited with pure hydrogen at 3.5 K to form the group 14 hydrides. The initial SiH(2) product reacts completely to SiH(4), whereas substantial proportions of GeH(2), SnH(2), and PbH(2) are trapped in solid hydrogen. Further hydrogen atom reactions form the trihydride radicals and tetrahydrides of Ge, Sn, and Pb. The observation of PbH(4) at 1815 cm(-)(1) and PbD(4) at 1302

  激光烧蚀的 Si、Ge、Sn 和 Pb 原子与纯氢在 3.5 K 下共沉积，形成 14 族氢化物。最初的 SiH(2) 产品与 SiH(4) 完全反应，而 GeH(2)、SnH(2) 和 PbH(2) 的很大比例被困在固体氢中。进一步的氢原子反应形成 Ge、Sn 和 Pb 的三氢化物自由基和四氢化物。1815 cm(-)(1) 处的 PbH(4) 和 1302 cm(-)(1) 处的 PbD(4) 的观察结果与这些不稳定的甲烷四氢化物类似物的量子化学计算的预测一致。此外，新的吸收被观察到 Pb(2)H(2) 和 Pb(2)H(4)，它们具有基于量子化学计算的双桥结构。
• Direct kinetic studies of SiH₃+SiH₃, H, CCl₄, SiD₄, Si₂H₆, and C₃H₆by tunable infrared diode laser spectroscopy
  作者：S. K. Loh、J. M. Jasinski

  DOI：10.1063/1.461707

  日期：1991.10

  Gas phase reactions of silyl radical, SiH3, are investigated at room temperature using tunable diode laser flash kinetic spectroscopy. Photolytic generation of silyl at 193 and 248 nm is demonstrated using several different precursor systems. The silyl recombination reaction, SiH3+SiH3→Si2H6, is studied by quantitative measurement of SiH3 and attendant product densities. Analysis yields a refinement of the rate constant, krc=(7.9±2.9)×10−11 cm3 molecule−1 s−1. By modeling silyl densities following photolysis of HCl in SiH4, bimolecular rate constants for H+SiH3 and H+SiH4 are determined to be (2±1)×10−11 and (2.5±0.5)×10−13 cm3 molecule−1 s−1, respectively. Reactions of SiH3 with SiD4, Si2H6, CCl4, and C3H6 (propylene) are studied under pseudo-first-order conditions. Derived upper limits to the rate constants show these reactions to be slow at room temperature. The data demonstrate the reactivity of silyl with open-shell (radical) species and the general inertness of silyl toward closed shell molecules. Under typical chemical vapor deposition conditions, SiH3 is, therefore, a kinetically long-lived species in the gas phase and consequently a potentially important film forming species under plasma and photochemical deposition conditions.
• Reactions of silicon clusters with silane-d4: formation of structural isomers
  作者：W. D. Reents、M. L. Mandich

  DOI：10.1021/j100321a040

  日期：1988.5