cis-Re(CO)4(P(O-i-Pr)3)I | 134770-92-6

• 英文名称: cis-Re(CO)4(P(O-i-Pr)3)I
• CAS: 134770-92-6；142560-37-0
• 化学式: C₁₃H₂₁IO₇PRe
• 分子量: 633.391
• InChiKey: IZPZIDZKMBGEPW-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：

  异氰酸叔丁酯 、 cis-Re(CO)4(P(O-i-Pr)3)I 在 palladium(II) oxide 作用下， 以 苯 为溶剂， 以16%的产率得到
  参考文献：
  名称：

  Isomers of Re(CO)3(CNtBu)LX: Synthetic strategies starting from MnRe(CO)8(CNtBu)L and Re(CO)4LX (X  halogen; L Group 15 donor ligand)

  摘要：

  Reaction of Re(CO)(4)LX (L = PMePh(2), PMe(2)Ph, PPh(3), P(OMe)(3), P((OPr)-Pr-i)(3), P(O-o-tol)(3); X = Br,I) with (t)BuNC in the presence of PdO catalyst gave the new complexes Re(CO)(3)(CN(t)Bu)LX in high yield(> 60%). The new complexes were shown by spectroscopic techniques (IR, H-1 and P-31 NMR) to comprise a mixture of mer and fac isomers. The mer/fac ratio decreased with reaction temperatures (e.g. L = P(OMe)(3); 10 degrees C, ratio = 3; 45 degrees C, ratio = 0.25). At high temperatures (90 degrees C) isomerization of the mer to the fac isomers (L = PMe(2)Ph, P(OMe)(3)) occurred, suggesting that the mer isomer was the kinetic product of the catalyzed reaction. Reactions induced by Me(3)NO gave similar effects. Halogen cleavage of MnRe(CO)(8)(CN(t)Bu)L, prepared from MnRe(CO)(9)(CN(t)Bu) and L in the presence of Me(3)NO, yielded either one or two isomers of Re(CO)3(CN(t)Bu)(L)X (X = I, Br; 40% yield). For large L (e.g. PPh(3)) a new mer isomer with L trans to X was synthesized, and characterized by IR and NMR spectroscopy. For small L (e.g. P(OMe)(3)) a mixture of the two different mer products was obtained. The product isomer ratio was determined predominantly by the position of L in the starting dimer.

  DOI：

  10.1016/0022-328x(94)87272-4
• 作为产物：
  描述：

  丙烯酰碘 、 Re(CO)4(P(O-i-Pr)3) 以 甲苯 为溶剂， 生成 cis-Re(CO)4(P(O-i-Pr)3)I
  参考文献：
  名称：

  Re(CO)4L自由基卤原子转移反应的性质

  摘要：

  铼羰基 Re(CO)/sub 4/L (L = P(CH/sub 3/)/sub 3/, P(OiC/sub 3/H/sub 7/)/sub 3/)，由 N 生成/sub 2/ 激光闪光光解，在双分子原子转移反应中与有机卤化物反应，形成 XRe(CO)/sub 4/L (X = Cl, Br, I)。在甲苯中以 22 /sup 0 / C 测量与 18 个有机卤原子供体反应的速率常数。速率常数与可用的热化学 CX 键能没有很好的相关性。一系列具有 Re(CO)/sub 4/P(OiC/sub 3/H/sub 7/)/sub 3/ 的苄基溴的溴原子转移的速率常数遵循哈米特方程相关性，rho = 0.75。数据很好地拟合了原子或电子转移的 Marcus/Agmon-Levine 方程，当有机卤化物的半波还原电位用作测速过程中相对整体自由能变化的量度时。Rehm-Weller 方程同样很好地适应了这些数据。L

  DOI：

  10.1021/ja00245a015

文献信息

• The PdO catalysed reaction between Re(CO)5X (X  Cl, Br, I) and L (L  Group 15 donor ligand). Synthesis of Re(CO)4LX
  作者：Ann E. Leins、Neil J. Coville

  DOI：10.1016/0022-328x(91)86314-g

  日期：1991.4

  Previously there has been no high yielding synthesis of Re(CO)4LX (L = Group 15 donor ligand, X = Cl, Br, I). We here show that the PdO-catalysed reaction between Re(CO)5X and L gives Re(CO)4LX in > 75% yield when L has a cone angle less than 150-degrees. The new complexes have been fully characterised by IR and H-1 NMR spectrscopy.
• Ingham, Wayne L.; Coville, Nell J., Organometallics, 1992, vol. 11, # 7, p. 2551 - 2558
  作者：Ingham, Wayne L.、Coville, Nell J.

  DOI：——

  日期：——