| 1034661-85-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 1034661-85-2
• 化学式: C₅₃H₅₆I₂N₄P₂Rh*I
• 分子量: 1294.62
• InChiKey: SKOVYKILWRXULW-UHFFFAOYSA-K

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：

  、 1,2-二氯乙烷 生成 、
  参考文献：
  名称：

  含螯合二卡宾和二膦配体的铑（III）配合物的合成，异构化和催化转移加氢活性

  摘要：

  Different rhodium(III) complexes [Rh(C,C)(P,P)X-2](+) bearing both a cis-chelating dicarbene and a diphosphine ligand were synthesized (C,C = methylene(4,4'-diimidazolylidene); P,P = 1,2-bis(diphenylphosphino)ethane (dppe), (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (R-BINAP); X = halide, carbanion, NCMe). Solution analysis by NMR spectroscopy indicate a dynamic behavior of the complexes and cis/trans isomerization processes, likely through dissociation of the nonchelating ligands X (X = halide, NCMe), and eventually also involving the diphosphine ligand, identified by the formation of phosphine oxides. The presence of a diphosphine ligand in addition to the dicarbene substantially enhances the catalytic activity of the rhodium center in the transfer hydrogenation of ketones in iPrOH/KOH, reaching over 4000 turnover numbers and turnover frequencies around 1000 h(-1) vs 330 h(-1) for the phosphine-free analogue. Optimization of the catalytic conditions allowed transfer hydrogenation to be run with only 1 mol % base instead of the often used 10 mol %. The chiral R-BINAP ligand enhances catalytic activity, though no enantioselectivity was induced in the transfer hydrogenation of fluoroacetophenone as prochiral substrate.

  DOI：

  10.1021/acs.organomet.5b00809
• 作为产物：
  描述：

  、 1,2-双(二苯基膦)乙烷 以 二氯甲烷 为溶剂， 以95%的产率得到
  参考文献：
  名称：

  含碳原子数为4的N-杂环卡宾的铑（III）配合物：合成，配位化学和转移氢化中的催化活性

  摘要：

  用RhCl 3或[RhCl（cod）] 2和KI直接金属化C2保护的二亚咪唑鎓盐，得到了一系列具有异常C4结合，顺式螯合的NHC配体的新的铑（III）配合物。将复合物分离为含有两个（μ二元金属物种2 -I）3 -bridged铑（III）中心。在配位配体如CH 3 CN，PPh 3或dppe的存在下，二聚体结构易于裂解并产生单金属络合物。代表性结构的晶体学分析表明较高的反式与正常NHC相比，异常结合C4的卡宾对碳氢化合物的影响。在这种C4配位模式下，羧甲烯具有极强的供体能力，从而提高了铑中心的催化活性，并实现了i PrOH / KOH中酮的有效转移加氢。

  DOI：

  10.1021/om800110c
• 作为试剂：
  描述：

  苯甲醛 在 、 异丙醇 、 potassium hydroxide 作用下， 以 水 为溶剂， 反应 2.0h， 以23%的产率得到苯甲醇
  参考文献：
  名称：

  含螯合二卡宾和二膦配体的铑（III）配合物的合成，异构化和催化转移加氢活性

  摘要：

  Different rhodium(III) complexes [Rh(C,C)(P,P)X-2](+) bearing both a cis-chelating dicarbene and a diphosphine ligand were synthesized (C,C = methylene(4,4'-diimidazolylidene); P,P = 1,2-bis(diphenylphosphino)ethane (dppe), (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (R-BINAP); X = halide, carbanion, NCMe). Solution analysis by NMR spectroscopy indicate a dynamic behavior of the complexes and cis/trans isomerization processes, likely through dissociation of the nonchelating ligands X (X = halide, NCMe), and eventually also involving the diphosphine ligand, identified by the formation of phosphine oxides. The presence of a diphosphine ligand in addition to the dicarbene substantially enhances the catalytic activity of the rhodium center in the transfer hydrogenation of ketones in iPrOH/KOH, reaching over 4000 turnover numbers and turnover frequencies around 1000 h(-1) vs 330 h(-1) for the phosphine-free analogue. Optimization of the catalytic conditions allowed transfer hydrogenation to be run with only 1 mol % base instead of the often used 10 mol %. The chiral R-BINAP ligand enhances catalytic activity, though no enantioselectivity was induced in the transfer hydrogenation of fluoroacetophenone as prochiral substrate.

  DOI：

  10.1021/acs.organomet.5b00809