| 185309-18-6

• CAS: 185309-18-6
• 化学式: C₁₄H₁₈CrO₃S
• 分子量: 318.357
• InChiKey: OLRPZYLBHJMCDW-UHFFFAOYSA-M

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：

  、 硫化氢 以 四氢呋喃 为溶剂， 生成 tricarbonyl(η5-pentamethylcyclopentadienyl)(hydrogensulfido)chromium
  参考文献：
  名称：

  硫插入金属氢键的焓。配合物HS-M（CO）（3）C（5）R（5）的合成，结构和量热研究[M = Cr，Mo，W; R = H，我]。

  摘要：

  报告了巯基配合物HS-M（CO）（3）C（5）R（5）（M = Cr，R = Me; M = Mo，W，R = H，Me）的合成和量热研究。Mo和W配合物可以通过氢化物配合物HM（CO）（3）C（5）R（5）与Ph（3）Sb = S的反应高收率获得，后者易于经历单个S原子转移至金属-氢键产生金属-巯基配合物。金属氢化物与有限量的硫之间的直接反应也产生作为主要有机金属产物的巯基配合物。在硫原子/金属氢化物比率高于1/1时，会检测到其他配制成HS（n）（）-M（CO）（3）C（5）R（5）的产物。已经通过溶液量热法确定了硫从Ph（3）Sb = S和S（8）插入金属-氢键的焓。HS-M（CO）（3）C（5）R（5）配合物（M = Mo，对于R = H，W）很容易被PCy（3）脱硫，对于R = Me，W）不易被脱硫。配合物HS-M（CO）（3）C（5）Me（5）的M-SH键强度估计按Cr（46）

  DOI：

  10.1021/ic981221x
• 作为产物：
  描述：

  (η5-C5Me5)Cr(CO)3 、 二甲基二硫 以 甲苯 为溶剂， 生成
  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