sulphonium | 14701-12-3

• 分子结构分类: 无机化合物 - 均质非金属化合物 - 均质其他非金属化合物
• 英文名称: sulphonium
• 英文别名: hydron;sulfane
• CAS: 14701-12-3
• 化学式: H₃S
• 分子量: 35.0898
• InChiKey: RWSOTUBLDIXVET-UHFFFAOYSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 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：
  1
• 氢给体数：
  1
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  sulphonium 、 三氟乙酸 生成
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: S: SVol.4a/b, 1.3.8.11.3, page 217 - 219

  摘要：

  DOI：
• 作为产物：
  描述：

  Phosphaniumyl 在 硫化氢 作用下， 以 neat (no solvent) 为溶剂， 生成 sulphonium
  参考文献：
  名称：

  A selected ion flow tube study of the reactions of the PH⁺_n ions (n=0 to 4) with several molecular gases at 300 K

  摘要：

  The reactions of ions in the series PH+n (n=0 to 4) have been studied at 300 K with CH3NH2, PH3, NH3, CH3CCH, H2S, C2H4, CH3OH, COS, C2H2, O2, H2O, CH4, HCN, CO2, CO, and H2 using a selected ion flow tube (SIFT) apparatus. The majority are fast binary reactions, the measured rate coefficients, k, being close to the respective collisional values, and for reactions involving polyatomic reactant molecules multiple product ions are observed. Most reaction mechanisms are represented in this large number of reactions including charge transfer, proton transfer, atom abstraction and especially evident is phosphorus atom insertion in which product ions such as HnPN+, HnPO+, HnPS+ and HnCmP+ are formed. The reactions of the PH+n ions (n=0 to 2) with CO2, CO, and H2 proceed by the process of ternary association except for the P+ reaction with CO2, in which PO+ is formed in a fast binary reaction. PH+4 reacts only with CH3NH2 and NH3 by fast proton transfer, a process which is always rapid when it is exothermic. Upper limits to the heats of formation of HPO+, H2PO+, PC2H2+ and HCP have also been deduced from their observation as products of some of the reactions.

  DOI：

  10.1063/1.456337
• 作为试剂：
  描述：

  苯 在 sulphonium 作用下， 生成 cyclohexa-1->5-dienylium
  参考文献：
  名称：

  Combined Experimental and Theoretical Study of the Protonation of Polyfluorobenzenes [C6H6-nFn] (n=0-6)

  摘要：

  In a recent high-pressure mass spectrometric revision to the gas-phase basicity scale (J. E. Szulejko and T. B. McMahon, J. Am. Chem, Soc. 115, 7839 (1993)), it was observed that the proton affinity for hexafluorobenzene was 24 kcal mol(-1) (1 kcal = 4.184 kJ) lower than the accepted National Institute of Science and Technology (NIST) database value of 177.7 kcal mol(-1) (S. G. Lias et al., J. Phys. Chem. Ref. Data 17, Suppl. 1 (1988)). Furthermore, the proton affinities for most other polyfluorobenzenes were also found to differ substantially from the NIST values, For many of the polyfluorobenzenes large protonation entropy changes were noted, which were substantially greater than then those expected from rotational symmetry number changes alone, In vies of these observations, MP2/6-31G(**)//HF/6-31G(**) ab initio calculations sere undertaken to investigate further the proton affinity and entropy changes with respect to the degree of fluorine substitution. The present proton affinity variations found for the polyfluorobenzenes (hexaflorobenzene excepted) can be interpreted with the aid of the ab initio results in terms of a simple additivity scheme. Each fluorine substituent para, meta, ortho or ipso to the ring protonation site will induce an incremental proton affinity change with respect to benzene of 1.5, -7.0, -1.5 and -19.0 kcal mol(-1), respectively, This additivity scheme can also be used to rationalize the re-evaluated proton affinities for the polymethylbenzenes and m- and o-fluorotoluenes. The corresponding methyl increments are 7.5, 5.5, 25 and 1.0 kcal mol(-1) for para, meta, ortho and ipso protonation respectively, From the present ab initio statistical thermodynamic analysis of the various protonation entropy components, it was concluded that the low-frequency vibrations are almost exclusively responsible for the large excess entropy changes observed experimentally. Ab initio calculated barriers for 1,2 proton shifts in arenium species available in the literature are concluded to be too large to allow the existence of a so-called dynamic proton. Large excess protonation entropies are noted from the literature for polymethylbenzenes, naphthalene and 1-methylnaphthalene. (C) 1997 by John Wiley & Sons, Ltd.

  DOI：

  10.1002/(sici)1096-9888(199705)32:5<494::aid-jms508>3.0.co;2-y

文献信息

• Gas phase basicities and relative proton affinities of compounds between water and ammonia from pulsed ion cyclotron resonance thermal equilibriums measurements
  作者：J. F. Wolf、R. H. Staley、I. Koppel、M. Taagepera、R. T. McIver、J. L. Beauchamp、R. W. Taft

  DOI：10.1021/ja00458a032

  日期：1977.8

  indicate that protonation is thermodynamically favored in the gas phase at the carbonyl oxygen of the latter. Large effects of polar electronegative substituents have been observed for various oxygen and nitrogen bases. An evaluation of entropy effects in gas phase proton transfer equilibria shows such effects to bemore » generally small for simple bases and approximately equal to entropy effects expected

  用于精确测定质子转移平衡常数的脉冲离子回旋共振方法已应用于 46 种碳、氮、氧、磷、硫、砷和硒碱，重复重叠序列，获得水和氨的相对质子亲和力. 在可能进行比较的情况下，结果通常与高压质谱法获得的结果一致。结果为分子结构对基础强度的内在影响提供了重要的新见解。说明了这些结果在导出其他气态离子热化学数据中的应用。特别是，甲基取代基对质子亲和力的影响已被广泛评估，并解释了与 n 碱共轭酸的均裂键解离能的相应影响和取代甲基阳离子的氢化物亲和力的比较。正烷基取代基对水和醇与​​羧酸及其酯的质子亲和力影响的比较表明，质子化在气相中在后者的羰基氧处是热力学有利的。对于各种氧和氮碱，已经观察到极性电负性取代基的巨大影响。对气相质子转移平衡中的熵效应的评估表明，这种效应对于简单的碱基通常较小，大约等于分子旋转对称数变化时预期的熵效应。最后，目前的结果为评估绝对质子亲和力和相对离子溶剂化能提供了基础。« 更少
• Reactions of CH+ ions ith molecules at 300 K
  作者：N.G. Adams、D. Smith

  DOI：10.1016/0009-2614(78)85278-6

  日期：1978.3

  The rate coefficients and product ion distributions have been obtained for the reactions of the CH+n ions (n = 0 to 4) with COS, H2S, H2CO, CH3OH and CH3NH2 in a SIFT at 300 K. The reactions are generally fast binary with multiple products except for CH+3 for which fast ternary association channels are also observed in parallel with the binary channels.

  在300°C的SIFT中，已获得CH + n离子（n = 0至4）与COS，H 2 S，H 2 CO，CH 3 OH和CH 3 NH 2的反应的速率系数和产物离子分布。 K.反应通常是具有多种产物的快速二元反应，但CH + 3除外，因为CH + 3的快速三元缔合通道也与二元通道平行观察到。
• Reactions of OH+ and H2O+ ions with some diatomic and simple polyatomic molecules
  作者：Z. Karpas、W.T. Huntress

  DOI：10.1016/0009-2614(78)85621-8

  日期：1978.11

  constants and product distributions of the reactions of OH+ and H2O+ with some diatomic and simple polyatomic molecules were studied by ion cyclotron resonance (ICR) mass spectrometric techniques. Reaction rates with CO, NO, O2, N2, CO2, H2S, N2O, H2CO, CH4 and CD4 were measured. Charge transfer and proton transfer were generally observed in cases for which the reaction channel is exothermic, but processes

  通过离子回旋共振（ICR）质谱技术研究了OH +和H 2 O +与一些双原子和简单多原子分子反应的速率常数和产物分布。测量与CO，NO，O 2，N 2，CO 2，H 2 S，N 2 O，H 2 CO，CH 4和CD 4的反应速率。通常在反应通道放热的情况下观察到电荷转移和质子转移，但未发现涉及重排的过程。
• Rate coefficients and product ion distributions for the reactions of OH+ and H2O+ with N2 , O2, NO. N2O, Xe, CO, CO2, H2S and H2 at 300 K
  作者：J.D.C. Jones、K. Birkinshaw、N.D. Twiddy

  DOI：10.1016/0009-2614(81)85191-3

  日期：1981.2

  product ion distribution for the reactions of OH+ and H2O+ with N2. O2.NO. N2O. Xe. CO, CO2. H2S and H2 have been determined at 294 ± 2 K using a selected ion flow tube (SIFT) apparatus. These reactions were generally found to proceed by either proton or chage transfer, or both, and for H2 by H-atom abstracticn. Revised limits for the proton affinities of N2, NO and Xe are suggested.

  OH +和H 2 O +与N 2反应的速率系数和产物离子分布。O 2否 Ñ 2 O.的Xe。CO，CO 2。H 2 S和H 2已使用选定的离子流管（SIFT）设备在294±2 K处测定。通常发现这些反应是通过质子转移或电荷转移，或两者同时进行，对于H 2是通过H原子抽象进行的。建议修改N 2，NO和Xe的质子亲和力极限。
• Measurements of the dissociative recombination coefficients for several polyatomic ion species at 300 K
  作者：Nigel G. Adams、David Smith

  DOI：10.1016/0009-2614(88)87081-7

  日期：1988.2

  The dissociative recombination coefficients, α, have been measured at 300 K for several polyatomic positive ion species using a flowing afterglow/Langmuir probe (FALP) apparatus. The α range from 1.1 × 10−7 cm3 s−1 for H2F+ to 2.2 × 10−6 cm3 s−1 for the clustered species H+(CH3OH)3. Several of the ionic species included in this study are considered to be involved in the synthesis of interstellar molecules

  使用流动的余辉/ Langmuir探针（FALP）装置，对几种多原子正离子物种在300 K下测量了离解重组系数α。对于H 2 F +，α的范围为1.1×10 -7 cm 3 s -1；对于簇状物种H +（CH 3 OH）3，α的范围为2.2×10 -6 cm 3 s -1。这项研究中包括的几种离子物质被认为与星际分子的合成有关。