trifluorosilanylium | 38192-99-3

• 分子结构分类: 无机化合物 - 均质非金属化合物 - 其他非金属卤化物
• 英文名称: trifluorosilanylium
• CAS: 38192-99-3
• 化学式: F₃Si
• 分子量: 85.0807
• InChiKey: JEZAFBTUBXYEBO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.34
• 重原子数：
  4.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  trifluorosilanylium 在 均三甲苯 作用下， 生成 硫酸盐离子
  参考文献：
  名称：

  Electron‐impact ionization cross sections of the SiF₃ free radical

  摘要：

  Absolute cross sections for electron-impact ionization of the SiF3 free radical from threshold to 200 eV are presented for formation of the parent SiF+3 ion and the fragment SiF+2, SiF+, and Si+ ions. A 3 keV beam of SiF3 is prepared by near-resonant charge transfer of SiF+3 with 1,3,5-trimethylbenzene. The beam contains only ground electronic state neutral radicals, but with as much as 1.5 eV of vibrational energy. The absolute cross section for formation of the parent ion at 70 eV is 0.67±0.09 Å2. At 70 eV the formation of SiF+2 is the major process, having a cross section 2.51±0.02 times larger than that of the parent ion, while the SiF+ fragment has a cross section 1.47±0.08 times larger than the parent. Threshold measurements show that ion pair dissociation processes make a significant contribution to the formation of positively charged fragment ions.

  DOI：

  10.1063/1.454836
• 作为产物：
  描述：

  silicon tetrafluoride 生成 trifluorosilanylium 、 氢氟酸
  参考文献：
  名称：

  Nonradiative decay pathways of electronic states of group IV tetrafluoro and tetrachloro molecular ions studied with synchrotron radiation

  摘要：

  The nonradiative decay channels of the valence electronic states of the gas-phase tetrahedral ions CF+4, SiF+4, CCl+4, SiCl+4, and GeCl+4 have been studied in the range 35–100 nm by a novel form of photoionization mass spectrometry. Tunable vacuum UV radiation from a synchrotron source ionizes the parent neutral molecule, and electrons and ions are detected by the photoelectron–photoion coincidence technique. The experiment is repeated continuously as a function of photon energy, and a three-dimensional histogram of photon energy versus ion time of flight versus coincidence count rate is produced. By taking cuts through this histogram, photoionization curves for the different fragment ions can be extracted. The appearance energies of the fragment ions (e.g., CF+2 from CF4, CCl+ from CCl4) occur at the adiabatic ionization potential of an electronic state of the parent ion, and not at the thermodynamic appearance energy of that ion. Attempts to measure the kinetic-energy releases in the fragmentation pathways have only been partially successful. The results are complementary to those of recent experiments to probe the radiative decay of these electronic states of MX+4 [M=C, Si, Ge; X=F, Cl] [J. Chem. Phys. 89, 2675 (1988); 89, 2683 (1988)], where the C̃ 2T2 and D̃ 2A1 third and fourth excited electronic states can show radiative decay to a surprising degree. The decay dynamics of the C̃ and D̃ states of MX+4 are reviewed. In general, the fluorides show different behavior to the analogous chlorides, and the carbon species behaves differently to the corresponding silicon or germanium species.

  DOI：

  10.1063/1.458810

文献信息

• Translational and internal energy effects in reactions of O+ and O+2 with SiF4
  作者：Ellen R. Fisher、P.B. Armentrout

  DOI：10.1016/0009-2614(91)87082-m

  日期：1991.5

  as a function of kinetic energy for reaction of SiF4 with O+(4S) and O+2 (2Πg, ν = O). Reactions of excited O+2 ions are also examined and are found to react more efficiently than ground state ions. The major reactions are dissociative charge transfer processes, although O+ also reacts to form OF + SiF+3 efficiently and O+2 reacts to form minor amounts of SiOF+x (x = 1−3).

  引导离子束技术被用于测量的横截面为动能为的SiF的反应的功能4为O +（4 S）和O + 2（2 Π克，ν= O）。还检查了激发的O + 2离子的反应，发现它们比基态离子更有效地反应。主要的反应是解离的电荷转移过程，尽管O +也有效地反应形成OF + SiF + 3，O + 2反应而形成少量的SiOF + x（x = 1-3）。
• Reactions of Ar⁺, Ne⁺, and He⁺with SiF₄from thermal energy to 50 eV c.m.
  作者：M. E. Weber、P. B. Armentrout

  DOI：10.1063/1.456016

  日期：1989.2.15

  Guided ion-beam techniques are used to measure the cross sections for reaction of SiF4 with Ar+, Ne+, and He+ from thermal to 50 eV. Charge transfer followed by loss of F atoms are the sole processes observed. All SiF+x (x=0–4) products are observed, except for SiF+4 from reaction with Ne+ and He+, and Si+ from reaction with Ar+. At high energies, the dominant products are SiF+3 in the Ar system, and SiF+ in both the Ne and He systems. There is some evidence in the Ne system for an excited state of SiF+3 at 5.7 eV. In the Ar+ and Ne+ reactions, the observed energetics are consistent with literature thermochemistry, but with He+, reaction barriers are observed. A value of ΔH0f,298 (SiF+3)=−30.1±0.9 kcal/mol is derived, which is in agreement with previous values but is much more precise. The observed product distributions and energetics are explained by consideration of the potential energy surfaces and the difference in ionization potentials of the rare gases. Finally, the relationships of these reactions to plasma deposition and etching are discussed.
• Energetics and dynamics in the reaction of Si⁺ with SiF₄. Thermochemistry of SiF_<i>x</i> and SiF⁺_<i>x</i> (<i>x</i>=1, 2, 3)
  作者：M. E. Weber、P. B. Armentrout

  DOI：10.1063/1.454387

  日期：1988.6

  The title reaction is studied using guided ion beam mass spectrometry. Absolute reaction cross sections are measured as a function of kinetic energy from thermal to 40 eV, and three endothermic product channels are observed. The dominant SiF++SiF3 channel is only slightly endothermic, while the SiF+3 +SiF and SiF+2 +SiF2 channels have much higher thresholds. The SiF+3 cross section magnitude is about half that of SiF+, while the SiF+2 cross section is an order of magnitude smaller than that of SiF+. A second feature which appears in the SiF+2 cross section is due to dissociation of SiF+3 . There is evidence that SiF+ and SiF+3 are produced via a direct mechanism. Competition between these two channels is interpreted in terms of molecular orbital correlations and qualitative potential energy surfaces. One surface is found to correlate only with the SiF+3 +SiF channel, while another correlates diabatically with this channel and adiabatically with the SiF++SiF3 channel. Competition on this latter surface has an energy dependence which is consistent with the Landau–Zener model. Reaction thresholds are analyzed to yield 298 K heats of formation for SiFx and SiF+x species. From an evaluation of these and literature values, we recommend the following values: ΔH0f(SiF+) =170.4±2.2 kcal/mol, IP(SiF)=7.54±0.16 eV, ΔH0f (SiF3)=−258±3 kcal/mol, and IP(SiF3)=9.99±0.24 eV.
• Experimental and Theoretical Studies of SiF<i>_n</i>(CO)₂⁺ Cations with <i>n</i> = 2 and 3:  A Search for Pentacoordinate Cationic Silicon
  作者：A. E. Ketvirtis、V. I. Baranov、A. C. Hopkinson、D. K. Bohme

  DOI：10.1021/jp970979j

  日期：1997.9.1

  The addition of carbon monoxide to the fluorosilicon cations SiF+, SiF2.+, and SiF3+ has been investigated in helium buffer gas at (294 +/- 3) K and (0.35 +/- 0.01) Torr using a selected-ion flow tube (SIFT) apparatus. The monofluorosilicon cation was found to be unreactive toward CO, whereas both the difluoro- and trifluorosilicon cations consecutively added two CO molecules. Molecular orbital calculations, using density functional theory (DFT) performed at the B-LYP/6-31G(d,p) level, showed that the lowest-energy isomer on the SiF3(CO)(2)(+) potential energy surface has a trigonal bipyramidal structure in which a pentacoordinate Si atom is surrounded by two axial CO ligands (bonded through C) and three equatorial F substituents. he ion at the global minimum on the SiF2(CO)(2)(.+) potential energy surface has a structure between that of a distorted tetrahedron and a trigonal bipyramid in which both CO molecules are axial and the two fluorine atoms and the unpaired electron are equatorial. Other low-lying isomers have trigonal bipyramidal structures in which one or both CO ligands are bonded to silicon through oxygenn or have tetrahedral structures in which an F3SiCO+ or F2SiOC.+ ion is solvated by CO. A multicollision-induced dissociation (CID) study of the product SiF3(CO)(2)(+) indicated the presence of at least three structural isomers, whereas the CID of SiF2(CO)(2)(.+) was less conclusive.