(OC)4Cr[η(2)-P(C6H5)2CH2CH2P(p-tolyl)2] | 79500-58-6

• 英文名称: (OC)4Cr[η(2)-P(C6H5)2CH2CH2P(p-tolyl)2]
• CAS: 79500-58-6
• 化学式: C₃₂H₂₈CrO₄P₂
• 分子量: 590.515
• InChiKey: SMSYVQWXCOSJKD-UHFFFAOYSA-N

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

• 作为产物：
  描述：

  (OC)5Cr[η(1)-P(C6H5)2CH2CH2P(C6H4CH3)2] 以 氘代甲苯 为溶剂， 生成 (OC)4Cr[η(2)-P(C6H5)2CH2CH2P(p-tolyl)2]
  参考文献：
  名称：

  Isomerization and Chelation Studies of (OC)₅M[η¹-PPh₂CH₂CH₂P(p-tolyl)₂] and (OC)₅M[η¹-P(p-tolyl)₂CH₂CH₂PPh₂] (M = Cr, Mo, W)

  摘要：

  Six dangling phosphine complexes have been synthesized to provide three pairs of linkage isomers, (OC)(5)M[eta (1)-PPh2CH2CH2P(p-tolyl)(2)] (3Cr, 3Mo, 3W) and (OC)(5)M[eta (1)-P(p-tolyl)(2)CH2CH2PPh2] (4Cr, 4Mo, 4W). Rate constants for isomerization in toluene of 3Cr, 3Mo, 3W, 4Cr, 4Mo, and 4W at 55 degreesC are 1.23 x 10(-8), 7.76 x 10(-6), 2.3 x 10(-8), 6.52 x 10(-9), 4.24 x 10(-6), and 9.7 x 10(-9) s(-1), respectively. Rate constants for chelation of 3Cr, 3Mo, 4Cr, and 4Mo are 1.15 x 10(-8), 3.9 x 10(-7), 1.23 x 10(-8), and 3.9 x 10(-7) s(-1), respectively. Chelation rates for 3W and 4W were too slow to conveniently measure. The position of equilibrium favors ditolylphosphino coordination with equilibrium constants of 1.88, 1.83, and 2.4 for the Cr, Mo, and W isomer pairs, respectively. Isomerization of 3Mo and 4Mo was studied at 25, 40, and 55 degreesC to give activation parameters, DeltaH(double dagger) and DeltaS(double dagger), of 102.4 and 103.6 kJ/mol and -32 and -33 J/(K mol), respectively, DeltaH(double dagger) and DeltaS(double dagger) for chelation of 3Mo and 4Mo were determined to be 113.5 and 115.5 kJ/mol and -22 and -16 J/(K mol), respectively. These results suggest that the transition states for both isomerization and chelation are significantly associative and become more so in descending order through group 6.

  DOI：

  10.1021/om000473e