PhSCr(CO)3(η5-C5Me5) | 185309-17-5

• 英文名称: PhSCr(CO)3(η5-C5Me5)
• CAS: 185309-17-5
• 化学式: C₁₉H₂₀CrO₃S
• 分子量: 380.428
• InChiKey: CULQCONBYZQLHZ-UHFFFAOYSA-M

计算性质

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

• 作为反应物：
  描述：

  PhSCr(CO)3(η5-C5Me5) 、 氧化亚氮 以 甲苯 为溶剂， 生成 (η5-C5Me5)Cr(NO)(CO)2
  参考文献：
  名称：

  * Cr（CO）（3）C（5）Me（5），HCr（CO）（3）C（5）Me（5）和PhSCr（CO）（3）C（）的反应动力学和热力学研究5）Me（5），带* NO。通过形成强Cr-NO键驱动的热力学上不稳定的分子HNO和RSNO的还原消除。

  摘要：

  H-Cr（CO）（3）C（5）Me（5）与* NO在1-2大气压下在甲苯溶液中反应生成Cr（NO）（CO）（2）C（5）Me（5）除了作为主要含氮产品的N（2）O和HNO（2）以外，还作为唯一含金属的产品。N（2）O和HNO（2）归因于初始产物HNO的分解。动力学研究得出速率定律d [P] / dt = -k（2nd）（）（阶）[HCr（CO）（3）C（5）Me（5）] [* NO]; k（2nd）（）（阶数）= 0.14 M（-）（1）s（-）（1）在10摄氏度时，DeltaH（）= 11.7 +/- 1.5 kcal / mol和DeltaS（）= -16.3 +/- 3.5 cal /（摩尔度）。反应速率不受CO的限制。D-Cr（CO）（3）C（5）Me（5）反应的动力学同位素效应为k（H）/ k（D）= 1.7。这些观察结果与第一步涉及从金属氢化物到* NO的直接H（D）原子转移形

  DOI：

  10.1021/ic990829i
• 作为产物：
  描述：

  (η5-C5Me5)Cr(CO)3 、 二苯二硫醚 以 甲苯 为溶剂， 生成 PhSCr(CO)3(η5-C5Me5)
  参考文献：
  名称：

  Reaction of Phenyl and Methyl Disulfide with ·Cr(CO)₃C₅Me₅ and HCr(CO)₃C₅Me₅. Metal Radical and Metal Hydride Reactivity at the Sulfur−Sulfur Bond. Different Mechanisms for Oxidative Addition of Alkyl and Aryl Disulfides

  摘要：

  The enthalpies of reaction of the . Cr(CO)(3)C(5)Me(5) and disulfides (RSSR) forming RS-Cr(CO)(3)C(5)Me(5) have been measured by solution calorimetry, Delta H = -13.3 + 1.5 kcal/mol (R = Ph) and -11.2 + 1.2 kcal/mol (R = Me). These data lead to Cr-SR bond strength estimates of 35 and 43 kcal/mol, respectively. The rates of oxidative addition have been investigated by FTIR spectroscopy. Phenyl disulfide reacts by a second-order mechanism whose rate-determining step is the attack of the chromium radical on the sulfur-sulfur bond, yielding chromium thiolate and a thiyl radical [k(298 K) 1.3 M(-1) s(-1), Delta H-phi = +10.2 kcal/mol, Delta S-phi = -24.4 cal/(mol deg)]. Methyl disulfide reacts by a third-order mechanism going through a termolecular transition state in which the stronger sulfur-sulfur bond in the alkyl disulfide is attacked simultaneously by two chromium radicals [k(298 K = 393 M(-2) s(-1), Delta H-phi = -0.2 kcal/mol, Delta S-phi = -47 cal/(mol deg)]. The rates of reaction of MeSSMe and PhSSPh with the hydride H-Cr(CO)(3)C(5)Me(5) have also been investigated in the presence of varying amounts of added . Cr(CO)(3)C(5)Me(5) radical. MeSSMe shows no apparent reaction with HCr(CO)(3)C(5)Me(5), even in the presence of added . Cr(CO)(3)C(5)Me(5). PhSSPh reacts with HCr(CO)(3)C(5)Me(5) primarily by a radical chain process involving . Cr(CO)(3)C(5)Me(5) and PhS . radicals. The upper limit to the rate of reaction by nonradical concerted addition is k(obs) < 4 x 10(-4) M(-1) s(-1).

  DOI：

  10.1021/ic960294i

文献信息

• Solution Calorimetric and Stopped-Flow Kinetic Studies of the Reaction of •Cr(CO)₃C₅Me₅ with PhSe−SePh and PhTe−TePh. Experimental and Theoretical Estimates of the Se−Se, Te−Te, H−Se, and H−Te Bond Strengths
  作者：James E. McDonough、John J. Weir、Matthew J. Carlson、Carl D. Hoff、Olga P. Kryatova、Elena V. Rybak-Akimova、Christopher R. Clough、Christopher C. Cummins

  DOI：10.1021/ic048321p

  日期：2005.5.1

  agreement with kinetic studies of H atom transfer from HSePh at higher temperatures. The reaction of H-Cr(CO)3C5Me5 with PhSe-SePh is accelerated by the addition of a Cr radical and occurs via a rapid radical chain reaction. In contrast, the reaction of PhTe-TePh and H-Cr(CO)3C5Me5 does not occur at any appreciable rate at room temperature, even in the presence of added Cr radicals. This is in keeping

  利用停止流技术研究了将PhSeSePh和PhTeTePh氧化添加到稳定的17电子配合物* Cr（CO）3C5Me5的动力学。每种反应物的反应速率均为一阶，活化焓从Se（deltaH（双匕首）= 7.0 +/- 0.5 kcal / mol，deltaS（double dagger）= -22 +/- 3降低eu）到Te（deltaH（双匕首）= 4.0 +/- 0.5 kcal / mol，deltaS（double dagger）= -26 +/- 3 eu）。PhSeH和* Cr（CO）3C5Me5的氧化加成动力学显示了从低温（整体为三阶）到高温（整体为二阶）的机理变化。已测量在甲苯溶液中将PhE-EPh氧化加成* Cr（CO）3C5Me5的焓，发现S，Se和Te分别为-29.6，-30.8和-28.9 kcal / mol。这些数据与动力学研究中的激活焓结合在一起，得出对于E = S
• Oxidative Addition of Butanethiol and Thiophenol to the ^•Cr(CO)₃C₅Me₅ Radical. Kinetic and Thermodynamic Study of a Third-Order Reaction and Its Catalysis
  作者：Telvin D. Ju、Russell F. Lang、Gerald C. Roper、Carl D. Hoff

  DOI：10.1021/ja960082k

  日期：1996.6.5