trans-Rh(CO)(i-Pr2HN)2Cl | 457608-44-5

• 英文名称: trans-Rh(CO)(i-Pr2HN)2Cl
• CAS: 457608-44-5
• 化学式: C₁₃H₃₀ClN₂ORh
• 分子量: 368.752
• InChiKey: WQBBTWYIRVLXEU-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：

  trans-Rh(CO)(i-Pr2HN)2Cl 以 solid matrix 为溶剂， 生成
  参考文献：
  名称：

  Photochemical intermediates of trans-Rh(CO)L2Cl where L=PMe3, PBu3, and i-Pr2HN and cis-Rh(CO)2(i-Pr2HN)Cl in frozen organic glasses

  摘要：

  The Nujol glass matrix photolyses of Rh(CO)(PMe3)(2)Cl (1), Rh(CO)(PBu3)(2)Cl (2), Rh(CO)(2)(i-Pr2HN)Cl (3), and Rh(CO)(i-Pr2HN)(2)Cl (4), have been examined. Phototolysis of 1 (lambda(irr) > 400 nm) and 2 (350 < lambda(irr) < 400 nm) give new species, A, with carbonyl stretching bands slightly below the parent bands. In the case of 1 this species appears to give rise to a second product, C, upon either extended photolysis or annealing, High-energy photolysis of 1, 2, and 4, result in loss of CO and formation of an IR silent species. RhL2Cl. In the case of 1 a new carbonyl species, B. is observed upon high-energy photolysis or annealing of a matrix containing CO and Rh(PMe3)(2)Cl. B may be converted to 1 by either back photolysis or annealing. Compound 3 undergoes photochemical CO-loss to form two isomeric photoproducts. Comparison of the carbonyl stretching frequencies of phosphine and ammine derivatives and photoproducts made it possible to eliminate PR, loss as the source of A. DFT calculations suggest that A may be a non-planar, triplet excited state of 1 or 2. DFT calculations also support the assignment of B to cis-Rh(CO)(PMe3)(2)Cl. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(02)01312-8
• 作为产物：
  描述：

  cis-[RhCl(CO)2(di-iso-propylamine)] 、 二异丙胺 以 正庚烷 为溶剂， 生成 trans-Rh(CO)(i-Pr2HN)2Cl
  参考文献：
  名称：

  Photochemical intermediates of trans-Rh(CO)L2Cl where L=PMe3, PBu3, and i-Pr2HN and cis-Rh(CO)2(i-Pr2HN)Cl in frozen organic glasses

  摘要：

  The Nujol glass matrix photolyses of Rh(CO)(PMe3)(2)Cl (1), Rh(CO)(PBu3)(2)Cl (2), Rh(CO)(2)(i-Pr2HN)Cl (3), and Rh(CO)(i-Pr2HN)(2)Cl (4), have been examined. Phototolysis of 1 (lambda(irr) > 400 nm) and 2 (350 < lambda(irr) < 400 nm) give new species, A, with carbonyl stretching bands slightly below the parent bands. In the case of 1 this species appears to give rise to a second product, C, upon either extended photolysis or annealing, High-energy photolysis of 1, 2, and 4, result in loss of CO and formation of an IR silent species. RhL2Cl. In the case of 1 a new carbonyl species, B. is observed upon high-energy photolysis or annealing of a matrix containing CO and Rh(PMe3)(2)Cl. B may be converted to 1 by either back photolysis or annealing. Compound 3 undergoes photochemical CO-loss to form two isomeric photoproducts. Comparison of the carbonyl stretching frequencies of phosphine and ammine derivatives and photoproducts made it possible to eliminate PR, loss as the source of A. DFT calculations suggest that A may be a non-planar, triplet excited state of 1 or 2. DFT calculations also support the assignment of B to cis-Rh(CO)(PMe3)(2)Cl. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(02)01312-8