(OC)5W[η(1)-P(C6H5)2CH2CH2P(C6H4CH3)2] | 213835-18-8

• 英文名称: (OC)5W[η(1)-P(C6H5)2CH2CH2P(C6H4CH3)2]
• 英文别名: (CO)5W(η(1)-PPh2CH2CH2P(p-tol)2)；(OC)5W[η(1)-P(p-tolyl)2CH2CH2P(C6H5)2]；(CO)5W(η(1)-P(p-tol)2CH2CH2PPh2)
• CAS: 213835-18-8；213835-23-5
• 化学式: C₃₃H₂₈O₅P₂W
• 分子量: 750.38
• InChiKey: HQKRLNNMLFFIOI-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：

  (OC)5W[η(1)-P(C6H5)2CH2CH2P(C6H4CH3)2] 以 氘代甲苯 为溶剂， 生成 (OC)4W[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
• 作为产物：
  描述：

  (CO)5W(P(p-tol)2H) 、 1,1-双(二苯基膦)乙烯 在 偶氮二异丁腈 作用下， 以 neat (no solvent) 为溶剂， 以44%的产率得到(OC)5W[η(1)-P(C6H5)2CH2CH2P(C6H4CH3)2]
  参考文献：
  名称：

  配位多膦的侧链基团诱导金属羰基中的膦交换加速。两个悬垂的磷化氢臂比一个悬臂要好得多1

  摘要：

  动力学和联动异构体的异构化的热力学（OC）5 W [η 1 -PPh 2 CH 2 CH（PPH 2）2 ]（1）和（OC）5 W [η 1 -PPh 2 CH（PPH 2）通过31 P { 1 H} NMR在10-55°C的温度范围内研究了氯仿中的CH 2 PPh 2 ]（2）。1到2的转化是放热的（ΔH = -12.25±0.1 kJ mol - 1），并伴随着熵的大幅降低（ΔS = -28.2±0.3 J mol - 1 K - 1）。该反应比预期的要快得多[ ķ =（1.18±0.01）×10 - 5个小号- 1 ]在25℃，并且其小活化焓（Δ ħ ⧧ = 92.6±1.9千焦耳摩尔- 1）和大的负激活熵（Δ小号⧧ = -28.2±6.2Ĵ摩尔- 1 ķ - 1）建议缔合机理。该反应是大小的4个数量比的异构化更快（OC）5 W [η 1 -PPh 2 CH 2 CH 2 P（p -Tol）2

  DOI：

  10.1021/om980289h