[phenyl(thiomethyl)carbene]pentacarbonylchromium(0) | 35797-96-7

• 英文名称: [phenyl(thiomethyl)carbene]pentacarbonylchromium(0)
• 英文别名: [phenyl(thiomethyl)carbene]pentacarbonylchromium(O)；(CO)5Cr=C(SMe)Ph
• CAS: 35797-96-7
• 化学式: C₁₃H₈CrO₅S
• 分子量: 328.266
• InChiKey: ISPPPTOKCLJMMP-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：

  [phenyl(thiomethyl)carbene]pentacarbonylchromium(0) 、 benzimidazolide 在 sodium perchlorate 作用下， 以 甲醇 为溶剂， 生成 [(CO)5Cr(C(benzimidazolyl)Ph)]
  参考文献：
  名称：

  Transition metal carbene chemistry7: Nucleophilic substitution reactions of imidazolide and benzimidazolide ions with Fischer carbene complexes in MeOH

  摘要：

  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.

  DOI：

  10.1016/j.jorganchem.2007.02.047
• 作为产物：
  描述：

  methanethiolate 、 pentacarbonyl(1-methoxybenzylidene)chromium(0) 以 甲醇 、 苯 为溶剂， 生成 [phenyl(thiomethyl)carbene]pentacarbonylchromium(0)
  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

• Physical Organic Chemistry of Transition Metal Carbene Complexes. 27. Substituent Effects on the Nucleophilic Substitution of [Aryl(thiomethyl)carbene]pentacarbonylchromium(0) Complexes by Amines in Aqueous Acetonitrile
  作者：Claude F. Bernasconi、Santanu Bhattacharya

  DOI：10.1021/om020955l

  日期：2003.3.1

  A kinetic study of the reactions of (CO)5CrC(SMe)C6H4Z (Z = 4-CF3, 4-Cl, 4-F, 4-Me, 4-MeO, and 4-Me2N) with n-butylamine, 2-chloroethylamine, piperidine, and 1-(2-hydroxyethyl)piperazine in 50% MeCN−50% water (v/v) at 25 °C is reported. In all cases the nucleophilic attachment of the amine to the carbene complex is rate limiting, which contrasts with the previously reported aminolysis of the methoxy

  （CO）5 Cr C（SMe）C 6 H 4 Z（Z = 4-CF 3，4 -Cl，4-F，4-Me，4-MeO和4-Me 2的反应动力学研究N）在25°C下于50％MeCN-50％水（v / v）中的正丁胺，2-氯乙胺，哌啶和1-（2-羟乙基）哌嗪进行了报道。在所有情况下，胺与卡宾配合物的亲核连接均受速率限制，这与先前报道的甲氧基类似物（（CO）5 Cr C（OMe）C 6 H 4Z），在大多数情况下，离开小组的离开是限速的。取代基对亲核连接步骤的影响（平均ρ= 0.55）比甲氧基类似物（ρ= 2.03）弱得多。结果表明，（CO）5 Cr C（SMe）C 6 H 4 Z的小ρ值是“正常”的，反映了在过渡态时取代基对部分正电荷和部分负电荷的作用几乎抵消。这些发现提供了证据：（CO）5 Cr C（OMe）C 6 H 4 Z的高ρ值是“异常的”，并且是甲氧基对反应物卡宾络合物的强烈π供体作用的结果。
• 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，
• Physical Organic Chemistry of Transition Metal Complexes. 31. Nucleophilic Attachment of the Malononitrile Anion to Fischer Carbene Complexes
  作者：Claude F. Bernasconi、Mahammad Ali

  DOI：10.1021/om0401051

  日期：2004.12.1

  CH(CN)2- to Fischer carbene complexes of the type (CO)5MC(XR)C6H4Z with M = Cr, W and XR = OMe, OEt, SMe in 50% MeCN−50% water (v/v) at 25 °C are reported. The malononitrile anion shows a much higher reactivity toward these carbene complexes than OH-, primary aliphatic amines (e.g. n-butylamine), or secondary alicyclic amines (e.g. piperidine) but is slightly less reactive than thiolate ions (e.g.

  速率常数为CH的附接（CN）2 -的式（CO）的费歇尔卡宾络合物5中号C（XR）C 6 H ^ 4，其中M =的Cr，W和XR = OME，OET，中小型50％Z据报道在25°C时MeCN-50％水（v / v）。丙二腈阴离子节目朝向这些卡宾络合物比OH高得多的反应性- ，脂族伯胺（例如Ñ丁胺），或仲脂环胺（例如哌啶），但略大于硫醇盐离子（例如HOCH反应性较低的2 CH 2小号-）。烷氧基卡宾配合物的反应比硫代甲基衍生物更快，这与先前对烷氧化物离子OH的发现一致-，胺和硫醇盐离子亲核试剂。与（CO）5 Cr C（SMe）C 6 H 4 Z反应的Hammettρ值为0.69，与（CO）5 Cr C（OMe）C 6 H 4 Z反应的Hammettρ值为2.88 。甲氧基卡宾配合物与以前在其他亲核试剂中观察到的模式相吻合，可以用甲氧基的π-给体效应来解释，该效应要比硫代甲基强得多。
• Physical Organic Chemistry of Transition Metal Carbene Complexes. 26. Kinetics and Mechanism of the Reactions of [Phenyl(thiomethyl)carbene]pentacarbonylchromium(0) with Amines in Aqueous Acetonitrile
  作者：Claude F. Bernasconi、Santanu Bhattacharya

  DOI：10.1021/om020748l

  日期：2003.2.1

  The kinetics of the reactions of (CO)5CrC(SMe)Ph (4-Cr) with five primary aliphatic and four secondary alicyclic amines have been investigated in 50% MeCN−50% water (v/v) at 25 °C. With n-butylamine, 2-methoxyethylamine, 2-chloroethylamine, glycinamide, piperidine, piperazine, and 1-(2-hydroxyethyl)piperazine, the reaction is strictly second order, i.e., first order in 4-Cr and first order in the amine

  （CO）5 Cr C（SMe）Ph（4-Cr）与5种伯脂族和4种仲脂环族胺在25°C下于50％MeCN-50％水（v / v）中反应的动力学进行了研究。与正丁胺，2-甲氧基乙胺，2-氯乙胺，甘氨酰胺，哌啶，哌嗪和1-（2-羟乙基）哌嗪相比，反应严格地是二级，即4-Cr中的一级和胺中的一级。与吗啉，由胺和被OH碱催化-观察，同时用氨基乙腈，OH -催化，但未检测到胺催化。这些结果可以通过三步反应机理来解释（方案1）：第一步是胺与卡宾配合物的亲核连接，形成两性离子中间体 ；第二步是快速的平衡去质子化 生成阴离子中间体 ; 第三步是MES -驱逐两个并行路径，MES中的一个是自发（溶剂催化）驱逐- ，另一个是RR ' NH 2 +催化MES的损失-从 。对于随后的二阶速率法的反应中，第一步是速率限制，而对于显示胺和/或OH的反应-催化，第三步是速率限制。详细讨论确定哪些步骤是速率限制的因素。
• Chemistry of transition metal carbene complexes: nucleophilic substitution reactions of cyanamide anion to Fischer carbene complexes
  作者：Sumana Gangopadhyay、Tarun Mistri、Malay Dolai、Rabiul Alam、Mahammad Ali

  DOI：10.1039/c2dt31454a

  日期：——

  higher reactivity and hence much higher ρ value for methoxy carbene complexes over the corresponding thiomethyl derivatives is best explained by considering the substituent effects not only on the transition state (TS) but also on the reactant, and consistent with the previously observed pattern. Higher k1(W)/k1(Cr) ratios for (thiomethyl)carbene complexes as well as methoxy and ethoxycarbene complexes

  氨基氰阴离子n的反应速率常数C-NH -与式（CO）的费歇尔卡宾络合物5中号C（XR）C 6 H ^ 4，其中M = Cr和W，XR = SME和OME Z，Z = NME 2，OME中，Me，H，F，Cl和CF 3中50％的MeCN-50％水报告了在25°C下的（v / v）。Ñ C-NH -显示对这些卡宾络合物比OH高得多的反应性- ，脂族伯胺（例如ñ丁胺）或脂环族仲胺（例如 哌啶），但略大于硫醇盐离子（反应性较低的例如HOCH 2 CH 2小号- ）。发现所述烷氧基卡宾配合物反应比硫代甲基衍生物，与烷氧离子之前的发现一致的速度更快，CH（CN）2 -，OH - ，胺和硫醇盐离子的亲核试剂。哈米特ρ的值是3.00±0.08（ķ 1）和2.98±0.08（ķ 2对Cr-OME-Z-N）C-NH -反应和0.94±0.05（ķ 1为）的Cr-SME-Z -N C- NH -反应。该ρ对于反