diphenylsilylene | 84960-82-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: diphenylsilylene
• 英文别名: SiMe2；SiPh2；Diphenylsilane
• CAS: 84960-82-7
• 化学式: C₁₂H₁₀Si
• 分子量: 182.297
• InChiKey: BPYFPNZHLXDIGA-UHFFFAOYSA-N

物化性质

• 保留指数：
  1441.8

计算性质

• 辛醇/水分配系数(LogP)：
  1.34
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• 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：

  diphenylsilylene 以 正己烷 为溶剂， 生成 tetraphenyldisilene
  参考文献：
  名称：

  Fast Kinetics Study of the Reactions of Transient Silylenes with Alcohols. Direct Detection of Silylene−Alcohol Complexes in Solution

  摘要：

  The kinetic behavior of dimethyl-, diphenyl-, and dimesitylsilylene in hexanes solution in the presence of methanol (MeOH), tert-butanol (t-BuOH), and the respective O-deuterated isotopomers has been studied, with the goal of elucidating a detailed mechanism for the formal O-H insertion reaction of transient silylenes with alcohols in solution. The data are in all cases consistent with a mechanism involving the intermediacy off lie corresponding silylene-alcohol Lewis acid-base complexes, which have been detected directly for each of the SiMe2-ROL and SiPh2-ROL (L = H or D) systems that were studied. Complexation proceeds effectively irreversibly (K-cq >= 2 x 10(5) M-1) and at close to the diffusion-controlled rate in these cases. I it contrast, the kinetic and spectroscopic behavior observed for SiMes(2) in the presence of these alcohols indicates the SiMes(2)-ROL complexes are involved its steady-state intermediates. Formed reversibly and 10-100 times more Slowly than is the case with SiMe2 and SiPh2 Product formation from the silylene-alcohol complexes is shown to proceed via catalytic proton transfer by it second molecule of alcohol, the rate of which exceeds that of unimolecular intracomplex H-migration in all cases, even at submillimolar alcohol concentrations. The catalytic rate constants range from 10(9) to 10(10) M-1 s(-1) for the SiMe2-ROH and SiPh2-ROH complexes, sufficiently fast that the isotope effect ranges from ca. 2.5 to close to unity for all but the SiPh2-t-BuOL complex, where it is remarkably large (k(HH)/k(DD)= 10.8 +/- 2.4). The value is consistent with a mechanism for catalysis involving double proton transfer within it cyclic five-membered transition state. The isotope effects on the ratio of the rate Constants for Catalytic proton transfer and dissociation of the SiMes(2)-MeOH and SiMes(2),-t-BuOH complexes suggest that a different mechanism for catalytic proton transfer is involved in the case of the sterically hindered diarylsilylene.

  DOI：

  10.1021/om9009747
• 作为产物：
  描述：

  1,1,3,3-tetramethyl-2,2-diphenyl-1,2,3-trisilacyclohexane 以 正己烷 为溶剂， 生成 diphenylsilylene
  参考文献：
  名称：

  来自瞬态亚硅烷与环氧乙烷和硫杂丙烷在溶液中反应的硅烷酮和硅烷硫酮。二苯基硅烷硫酮的直接检测。

  摘要：

  瞬态亚硅烷 SiMe(2) 和 SiPh(2) 与环己烯氧化物 (CHO)、环氧丙烷 (PrO) 和硫化丙烯 (PrS) 在烃溶剂中反应，形成与相应瞬态硅烷酮和硅烷硫酮的形成一致的产物，分别。激光闪光光解研究表明，这些反应通过多步序列进行，涉及相应的亚甲硅烷-环氧乙烷或硫杂丙环配合物的中间体，这些配合物在所有情况下都以接近扩散极限的速率常数形成，并表现出类似于与非反应性 O-和 S-供体、四氢呋喃和四氢噻吩的相应配合物。SiMe(2)-PrO 和 SiPh(2)-PrO 复合物的寿命都为约。300 ns，比相应的 CHO 复合物寿命更长，两者都在 230-240 ns 的范围内。另一方面，亚甲硅烷基-PrS 配合物的寿命要短得多，并且随甲硅烷基取代基而变化；SiMe(2)-PrS 复合物随激发激光脉冲衰减 (即 τ ≤ 25 ns)，而 SiPh(2)-PrS 复合物的 τ = 48 ± 3

  DOI：

  10.1021/ja107881p

文献信息

• Kinetics and mechanisms of the reactions of transient silylenes with amines
  作者：Svetlana S. Kostina、Tishaan Singh、William J. Leigh

  DOI：10.1002/poc.1908

  日期：2011.10

  constants for amine‐catalyzed H‐migration, which is thought to be the dominant mechanism for product formation from the complexes. The results are compared to published kinetic data for the O–H insertion reactions of these silylenes with alcohols, which also proceeds via initial complexation followed by catalytic proton transfer. The results indicate that catalyzed H‐transfer in the amine complexes is

  通过在正己烷中稳定地研究了二甲基，二苯基和二甲基苯乙烯基甲硅烷基（SiMe 2，SiPh 2和SiMes 2）与正丁胺（BuNH 2）和二乙胺（Et 2 NH）的N–H插入反应。状态和激光光解方法。该过程始于相应的路易斯酸碱配合物的形成，该配合物以二阶动力学衰减，其速率显示出对甲硅烷基和胺结构的适度敏感性。络合过程，也使用三乙胺进行了研究（Et 3N），以接近扩散极限的速率进行，但是速率常数随胺中的空间体积而系统地变化。确定了Et 2 NH和Et 3 N与SiMes 2的络合物的平衡常数，该络合物可逆地进行。SiMe 2和SiPh 2与BuNH 2和Et 2 NH的复合物以10 4 –10 5  s -1范围内的伪一级速率系数衰减。这与大约10 6  M –1  s –1的上限一致胺催化的H迁移的速率常数，这被认为是由络合物形成产物的主要机理。将结果与已公开的这些亚甲硅烷基与醇的O-H插入
• Silanones and Silanethiones from the Reactions of Transient Silylenes with Oxiranes and Thiiranes in Solution. The Direct Detection of Diphenylsilanethione.
  作者：Svetlana S. Kostina、William J. Leigh

  DOI：10.1021/ja107881p

  日期：2011.3.30

  basis of its second order decay kinetics and absolute rate constants for reaction with methanol, tert-butanol, acetic acid, and n-butyl amine, for which values in the range of 1.4 × 10(8) to 3.2 × 10(9) M(-1) s(-1) are reported. The experimental rate constants for decay of the SiMe(2)-epoxide and -PrS complexes indicate free energy barriers (ΔG(‡)) of ca. 8.5 and ≤7.1 kcal mol(-1) for the rate-determining

  瞬态亚硅烷 SiMe(2) 和 SiPh(2) 与环己烯氧化物 (CHO)、环氧丙烷 (PrO) 和硫化丙烯 (PrS) 在烃溶剂中反应，形成与相应瞬态硅烷酮和硅烷硫酮的形成一致的产物，分别。激光闪光光解研究表明，这些反应通过多步序列进行，涉及相应的亚甲硅烷-环氧乙烷或硫杂丙环配合物的中间体，这些配合物在所有情况下都以接近扩散极限的速率常数形成，并表现出类似于与非反应性 O-和 S-供体、四氢呋喃和四氢噻吩的相应配合物。SiMe(2)-PrO 和 SiPh(2)-PrO 复合物的寿命都为约。300 ns，比相应的 CHO 复合物寿命更长，两者都在 230-240 ns 的范围内。另一方面，亚甲硅烷基-PrS 配合物的寿命要短得多，并且随甲硅烷基取代基而变化；SiMe(2)-PrS 复合物随激发激光脉冲衰减 (即 τ ≤ 25 ns)，而 SiPh(2)-PrS 复合物的 τ = 48 ± 3
• Fast Kinetics Study of the Reactions of Transient Silylenes with Alcohols. Direct Detection of Silylene−Alcohol Complexes in Solution
  作者：William J. Leigh、Svetlana S. Kostina、Adroha Bhattacharya、Andrey G. Moiseev

  DOI：10.1021/om9009747

  日期：2010.2.8

  The kinetic behavior of dimethyl-, diphenyl-, and dimesitylsilylene in hexanes solution in the presence of methanol (MeOH), tert-butanol (t-BuOH), and the respective O-deuterated isotopomers has been studied, with the goal of elucidating a detailed mechanism for the formal O-H insertion reaction of transient silylenes with alcohols in solution. The data are in all cases consistent with a mechanism involving the intermediacy off lie corresponding silylene-alcohol Lewis acid-base complexes, which have been detected directly for each of the SiMe2-ROL and SiPh2-ROL (L = H or D) systems that were studied. Complexation proceeds effectively irreversibly (K-cq >= 2 x 10(5) M-1) and at close to the diffusion-controlled rate in these cases. I it contrast, the kinetic and spectroscopic behavior observed for SiMes(2) in the presence of these alcohols indicates the SiMes(2)-ROL complexes are involved its steady-state intermediates. Formed reversibly and 10-100 times more Slowly than is the case with SiMe2 and SiPh2 Product formation from the silylene-alcohol complexes is shown to proceed via catalytic proton transfer by it second molecule of alcohol, the rate of which exceeds that of unimolecular intracomplex H-migration in all cases, even at submillimolar alcohol concentrations. The catalytic rate constants range from 10(9) to 10(10) M-1 s(-1) for the SiMe2-ROH and SiPh2-ROH complexes, sufficiently fast that the isotope effect ranges from ca. 2.5 to close to unity for all but the SiPh2-t-BuOL complex, where it is remarkably large (k(HH)/k(DD)= 10.8 +/- 2.4). The value is consistent with a mechanism for catalysis involving double proton transfer within it cyclic five-membered transition state. The isotope effects on the ratio of the rate Constants for Catalytic proton transfer and dissociation of the SiMes(2)-MeOH and SiMes(2),-t-BuOH complexes suggest that a different mechanism for catalytic proton transfer is involved in the case of the sterically hindered diarylsilylene.