(CO)5Cr=W(SMe)Ph | 52843-33-1

• 英文名称: (CO)5Cr=W(SMe)Ph
• CAS: 52843-33-1
• 化学式: C₁₃H₈O₅SW
• 分子量: 460.12
• InChiKey: SGLZBYKGVBORGS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (CO)5Cr=W(SMe)Ph 以 乙醚 为溶剂， 生成 乙腈(五羰基)钨(0)
  参考文献：
  名称：

  形式化的氢化氮插入Fischer型卡宾络合物的金属卡宾键中

  摘要：

  DOI：

  10.1021/om00151a028
• 作为产物：
  描述：

  以 水 、 乙腈 为溶剂， 生成 (CO)5Cr=W(SMe)Ph
  参考文献：
  名称：

  Physical Organic Chemistry of Transition Metal Carbene Complexes. 17.¹ Kinetics of the Reactions of (Arylthioalkoxycarbene)pentacarbonyl Complexes of Chromium(0) and Tungsten(0) with Thiolate Ions in Aqueous Acetonitrile:  pK_a Values of the Metal-Protonated Tetrahedral Adducts Formed between Carbene Complexes and Thiolate Ion

  摘要：

  Rate and equilibrium constants for the nucleophilic attachment of various thiolate ions to (CO)(5)M= C(SMe)Ph (M = Cr and W) and for the attachment of HOCH2CH2S- to (CO)(5)W=C(SCH2CH2OH)C(6)H(4)Z (Z = CF3, Cl, F, H, Me, MeO, and Me2N) have been determined in 50% MeCN-50% water (v/v) at 25 degrees C. For some of the adducts, those of the general structure (CO)(5)MC(SR,SR')C(6)H(4)Z, a kinetic determination of the pK(a) of their metal-protonated conjugate acid, (CO)(5)M(H)C(SR,SR')C(6)H(4)Z, is also reported. On the basis of Br phi nsted coefficients, Hammett rho values and comparisons with the reactions of the same thiolate ions with methoxy carbene complexes such as (CO)(5)M=C(OMe)Ph, insights into the role played by desolvation of the nucleophile prior to C-S bond formation, by the smaller pi-donor and inductive but larger steric effects of the MeS compared to the MeO group, by transition state imbalances, etc. are discussed. The pK(a) values obtained for (CO)(5)M(H)C(SR,SR')C(6)H(4)Z were used to resolve a mechanistic ambiguity in the hydrolysis of Fischer carbenes that have acidic protons on the alpha-carbon, e.g., (CO)(5)Cr=C(OMe)Me.

  DOI：

  10.1021/ja992741+

文献信息

• Transition Metal Carbene Chemistry. 4. Nucleophilic Attachment of DABCO to Fischer Carbene Complexes in MeCN
  作者：Mahammad Ali、Abhijit Dan、Ambarish Ray、Kaushik Ghosh

  DOI：10.1021/ic050349t

  日期：2005.8.1

  donor effect and partly due to steric crowding exerted by the slightly larger ethoxy group in the transition state. Higher k(1)(W)/k(1)(Cr) ratios for (thiomethyl)carbene complexes than methoxy or ethoxycarbene complexes are related to the intrinsic rate constant which is higher for ((thiomethyl)carbene)tungsten complexes than the corresponding Cr ones resulting in an enhanced ratio.

  DABCO（1,4-二氮杂双环[2.2.2]辛烷）与（CO）（5）Cr = C（XR）C（6）H（4）Z（X报道了在25摄氏度的干燥MeCN中的O和S）。对于具有（CO）（5）Cr = C（OMe）C（6）H（4）Z（10-Cr-Z）和（CO ）（5）Cr = C（SMe）C（6）H（4）Z（11-Cr-Z）。在50％MeCN-50％H（2）O（v / v）中10-Cr-Z和11-Cr-Z与CH（CN）（2）（-）反应的rho值可与目前的反应。DABCO与10-Cr-Z的反应与（n-Bu）（3）P与（CO）（5）W = C（OMe）C（6）H（5）-Z的反应更紧密相关（23）也提供了rho值2.22。与相应的硫代甲基衍生物相比，更高的rho值和因此更高的甲氧基碳烯配合物的反应性符合先前观察到的醇盐离子的模式，OH（-），胺和硫醇盐离子亲核试剂，合理的解释来自对取代基的影响，不仅考虑过渡态，
• Ali, Mahammad, Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 2005, vol. 44, # 9, p. 1817 - 1821
  作者：Ali, Mahammad

  DOI：——

  日期：——
• Physical Organic Chemistry of Transition Metal Carbene Complexes. 21.¹ Kinetics and Mechanism of Hydrolysis of (CO)₅MC(SR)Ar (M = Cr and W; R = CH₃ and CH₃CH₂CH₂; Ar = C₆H₅ and 3-ClC₆H₄) in Aqueous Acetonitrile. Important Differences Relative to Complexes with Alkoxy Leaving Groups
  作者：Claude F. Bernasconi、Gabriel S. Perez

  DOI：10.1021/ja002371l

  日期：2000.12.1

  A kinetic study of the hydrolysis of (CO)(5)M=C(SMe)Ph (M = Cr and W) in 50% MeCN-50% water (v/v) at 25 degreesC over a pH range from 1.7 to 14.2 is reported. The reaction occurs in two stages: the first is formation of (CO)(5)M=C(O-)Ph or (CO)(5)M=C(OH)Ph while the second stage leads to the formation of PhCH=O and (CO)(5)MOH-. This paper is concerned with the first stage. The rate-pH profiles are complex and consistent with a mechanism (Scheme 1) that involves water/OH- addition to the substrate to form a tetrahedral intermediate (T-OH(-)), followed by product formation via five potential pathways whose relative importance depends on the pH. A more limited study of the reactions of (CO)(5)M=C(SCH2CH2CH3)Ph (M = Cr and W) and (CO)(5)M=C(SMe)C6H4-3-Cl (M = Cr and W) with OH- is also reported. The main focus of the discussion is aimed at understanding the reactivity differences between (CO)(5)M=C(SMe)Ph and the corresponding methoxy analogues studied earlier. This understanding is in large measure based on an analysis of how the intrinsic rate constants are affected by the interplay of steric, inductive, and pi -donor effects and the potential imbalances of these effects at the transition state. It is also shown that the much lower sensitivity to H+-catalysis of RS- compared to RO- leaving group departure from the tetrahedral intermediate is responsible for the more complex rate-pH profile for the hydrolysis of (CO)(5)M=C(SMe)Ph than for the hydrolysis of the methoxy analogue.
• Transition metal carbene chemistry7: Nucleophilic substitution reactions of imidazolide and benzimidazolide ions with Fischer carbene complexes in MeOH
  作者：Supriya Biswas、Mahammad Ali

  DOI：10.1016/j.jorganchem.2007.02.047

  日期：2007.6

  Rate constants for the nucleophilic substitution reactions of imidazolide (IZ(-)) and benzimidazolide (BIZ(-)) ions with 4-Cr-Z and 5 in MeOH at 25 degrees C are reported and Hammett rho values are evaluated to be 1.50 +/- 0.10 and 1.51 +/- 0.08 for 4-Cr-Z-IZ(-) and 4-Cr-Z-BIZ(-) reactions, respectively. The comparable reactivity and also almost identical rho values for these reactions indicate that there is no difference in sensitivity towards electronic effects due to slightly bigger size of BIZ(-) over IZ(-) and bond formation at the transition states are equally progressed. The higher rho values for these reactions compared to those with a wide range of nucleophiles may arise mainly due to lower polarity of the solvent MeOH which enhances the requirement for stabilization of the negative charge in the transition state by the Z-substituents. (C) 2007 Elsevier B.V. All rights reserved.