iridium(3+);2-(4-methylphenyl)sulfonylazanidylacetate;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;triphenylphosphane | 167424-50-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: iridium(3+);2-(4-methylphenyl)sulfonylazanidylacetate;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;triphenylphosphane
• CAS: 167424-50-2
• 化学式: C₃₇H₃₉IrNO₄PS
• 分子量: 816.981
• InChiKey: AXHZOJKEBMPCGX-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  45
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  83.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  iridium(3+);2-(4-methylphenyl)sulfonylazanidylacetate;1,2,3,4,5-pentamethylcyclopenta-1,3-diene 、 三苯基膦 以 氘代氯仿 为溶剂， 以97%的产率得到iridium(3+);2-(4-methylphenyl)sulfonylazanidylacetate;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;triphenylphosphane
  参考文献：
  名称：

  配位不饱和CpIr-氨基酸复合物的形成和结构。高非对映选择性络合反应的动力学和热力学控制

  摘要：

  Amino acid derivatives bearing an electron-withdrawing group Z on N (Z = tosyl, CO2-CH(2)Ph, or acetyl) serve as (N,O)-chelating, dianionic ligands to the fragment Cp*Ir. Six such complexes have been prepared, all of them coordinatively unsaturated yet air-stable. The structure of the N-tosylglycine derivative C19H24IrNO4S (5a) was analyzed at 20 degrees C. A planar chelate ring was revealed, and relatively short Ir-N and Ir-O bonds suggested stabilization of unsaturated Ir by pi-donation. Crystals of the (R)-N-tosylphenylglycine complex C25H28IrNO4S (5f) were monoclinic. Some distortion of the chelate ring was seen, and both aryl rings were syn, the angle between their mean planes being 19 degrees. Within seconds, red solutions of the unsaturated complexes 5 turn yellow on addition of ligands such as phosphines, CO, and primary aliphatic or heterocyclic amines. Ligands add to chiral complexes so as to place the amino acid side chain R and Cp* cis to each other on the metallacycle, suggesting preferred approach of the ligand to 5 from the side opposite R. For one PMe(3) adduct this was shown to be the result of kinetic control (greater than or equal to 50:1 selectivity at 25 degrees C) and thermodynamic control (40:1 selectivity after equilibration at 90 degrees C, half-life = 5 h). PPh(3) and amines exchange within minutes at 25 degrees C. The stereoselectivity of ligand addition was highest for smaller ligands. Comparing this result and previous work suggests that steric interactions between added ligand and the amino acid side chain R determine diastereoselectivity.

  DOI：

  10.1021/om00008a014