iridium(3+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene;2-(pyridin-2-ylmethylsulfanyl)pyridine;chloride;hexafluorophosphate | 1370621-01-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: iridium(3+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene;2-(pyridin-2-ylmethylsulfanyl)pyridine;chloride;hexafluorophosphate
• CAS: 1370621-01-4
• 化学式: C₂₁H₂₅ClIrN₂S*F₆P
• 分子量: 710.146
• InChiKey: KYGTYKJOEKKLBH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  33
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  51.1
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  ammonium hexafluorophosphate 、 bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 、 2-((pyridin-2-ylsulfide)methyl)pyridine 以 甲醇 为溶剂， 以85%的产率得到iridium(3+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene;2-(pyridin-2-ylmethylsulfanyl)pyridine;chloride;hexafluorophosphate
  参考文献：
  名称：

  Efficient Catalysis of Transfer Hydrogenation of Ketones and Oxidation of Alcohols with Newly Designed Half-Sandwich Rhodium(III) and Iridium(III) Complexes of Half-Pincer Chalcogenated Pyridines

  摘要：

  The in situ generated ArE- (E = S or Se) reacts with (2-chloromethyl)pyridine in N-2 atmosphere, resulting in half-pincer (N, S/Se) ligands (2-arylchalcogenomethyl)pyridine (L1-L3; aryl = Ph/2-pyridyl for S, Ph for Se). Half-sandwich complexes [(eta(5)-Cp*)Rh(L)Cl][PF6] (1, 2), [(eta(5)-Cp*)Rh(L2)CH3CN]PF6](2) (3), and [(eta(5)-Cp*)Ir(L)Cl][PF6] (4-6), where L = L1-L3, have been synthesized by reacting L with [(eta(5)-Cp*)RhCl(mu-Cl)](2) and [(eta(5)-Cp*)IrCl(mu-Cl)](2) respectively. The ligands and complexes have been characterized by IR, HR-MS, and H-1, C-13{H-1}, and Se-77{H-1} NMR spectra. The single-crystal structures of all the complexes (1-6) have been determined with X-ray crystallography [Rh-S, Rh-Se, Ir-S, Ir-Se bond distances: 2.383(2)12.353(2), 2,4867(9), 2.343(2)/2.341(3), 2.453(1) angstrom, respectively]. Each metal has pseudo-octahedral half-sandwich "piano-stool" geometry. The PF6- ions in crystals are packed between half-sandwich complex molecules, resulting in various H center dot center dot center dot F secondary interactions. Complexes 1-6 have been explored for catalysis of oxidation of secondary alcohols with N-methylmorpholine-N-oxide and transfer hydrogenation reaction of ketones with 2-propanol and found very efficient, as revealed by TON values, which are up to 9.6 X 10(3) and 9.8 X 10(3) respectively for the two catalytic reactions. The formation of the M H bond has been noticed in the intermediates of both the catalytic reactions. DFT calculations indicate a reactivity order for the complexes of Rh > Ir, which is also found for the two catalytic reactions experimentally. The calculated (DFT) and observed bond distances and angles of 1-6 are reasonably close.

  DOI：

  10.1021/om300169p