CpFe(1,4-diphenyl-1,4-diphosphacycloheptane)Cl | 1370004-18-4

• 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: CpFe(1,4-diphenyl-1,4-diphosphacycloheptane)Cl
• 英文别名: cyclopenta-1,3-diene;(1S,4R)-1,4-diphenyl-1,4-diphosphepane;iron(2+);chloride
• CAS: 1370004-18-4
• 化学式: C₂₂H₂₅ClFeP₂
• 分子量: 442.688
• InChiKey: GOJQQWSOTNSANQ-LDQQLHBLSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.41
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  CpFe(1,4-diphenyl-1,4-diphosphacycloheptane)Cl 、 lithium aluminium tetrahydride 以 四氢呋喃 为溶剂， 以74%的产率得到CpFe(1,4-diphenyl-1,4-diphosphacycloheptane)(H)
  参考文献：
  名称：

  Synthesis, Characterization, and Reactivity of Fe Complexes Containing Cyclic Diazadiphosphine Ligands: The Role of the Pendant Base in Heterolytic Cleavage of H₂

  摘要：

  The iron complexes CpFe((P2N2Bn)-N-Ph)CI (1-CI), CpFe((P2N2Ph)-N-Ph)CI (2-CI), and CpFe((P2C5)-C-Ph)CI (3-CI) (where (P2N2Bn)-N-Ph is 1,5-dibenzyl-1,5-diaza-3,7-diphenyl-3,7-diphosphacyclooctane, (P2N2Ph)-N-Ph is 1,3,5,7-tetrapheny1-1,5-diaza-3,7-diphosphacyclooctane, and (P2C5)-C-Ph is 1,4-diphenyl-1,4-diphosphacycloheptane) have been synthesized and characterized by NMR spectroscopy, electrochemical studies, and X-ray diffraction. These chloride derivatives are readily converted to the corresponding hydride complexes [CpFe-((P2N2Bn)-N-Ph)H (1-H), CpFe((P2N2Ph)-N-Ph)H (2-H), CpFe((P2C5)-C-Ph)H (3-H)] and H-2 complexes [CpFe((P2N2Bn)-N-Ph)(H-2)]BAr4F, [1-H-2]BAr4F, (where BAr4F is B[(3,5-(CF3)(2)C6H3)(4)](-)), [CpFe((P2N2Ph)-N-Ph)(H-2)]BAr4F, [2-H-2]BAr4F, and [CpFe((P2C5)-C-Ph)(H-2)]-BAr4F, [3-H-2]BAr4F, as well as [CpFe((P2N2Bn)-N-Ph)(CO)]BAr4F, [1-CO]CI. Structural studies are reported for [1-H-2]BAr4F, 1-H, 2-H, and [1-CO]CI. The conformations adopted by the chelate rings of the (P2N2Bn)-N-Ph ligand in the different complexes are determined by attractive or repulsive interactions between the sixth ligand of these pseudo-octahedral complexes and the pendant N atom of the ring adjacent to the sixth ligand. An example of an attractive interaction is the observation that the distance between the N atom of the pendant amine and the C atom of the coordinated CO ligand for [1-CO]BAr4F is 2.848 angstrom, considerably shorter than the sum of the van der Waals radii of N and C atoms. Studies of H/D exchange by the complexes [1-H-2](+), [2-H-2](+), and [3-H-2](+) carried out using H-2 and D-2 indicate that the relatively rapid H/D exchange observed for [1-H-2](+) and [2-H-2](+) compared to [3-H-2](+) is consistent with intramolecular heterolytic cleavage of H-2 mediated by the pendant amine. Computational studies indicate a low barrier for heterolytic cleavage of H-2. These mononudear Fe-II dihydrogen complexes containing pendant amines in the ligands mimic crucial features of the distal Fe site of the active site of the [FeFe]-hydrogenase required for H-H bond formation and cleavage.

  DOI：

  10.1021/ja211193j
• 作为产物：
  描述：

  二氯四吡啶铁(II) 、 1,4-diphenyl-1,4-diphosphacycloheptane 以 甲苯 为溶剂， 以61%的产率得到CpFe(1,4-diphenyl-1,4-diphosphacycloheptane)Cl
  参考文献：
  名称：

  Synthesis, Characterization, and Reactivity of Fe Complexes Containing Cyclic Diazadiphosphine Ligands: The Role of the Pendant Base in Heterolytic Cleavage of H₂

  摘要：

  The iron complexes CpFe((P2N2Bn)-N-Ph)CI (1-CI), CpFe((P2N2Ph)-N-Ph)CI (2-CI), and CpFe((P2C5)-C-Ph)CI (3-CI) (where (P2N2Bn)-N-Ph is 1,5-dibenzyl-1,5-diaza-3,7-diphenyl-3,7-diphosphacyclooctane, (P2N2Ph)-N-Ph is 1,3,5,7-tetrapheny1-1,5-diaza-3,7-diphosphacyclooctane, and (P2C5)-C-Ph is 1,4-diphenyl-1,4-diphosphacycloheptane) have been synthesized and characterized by NMR spectroscopy, electrochemical studies, and X-ray diffraction. These chloride derivatives are readily converted to the corresponding hydride complexes [CpFe-((P2N2Bn)-N-Ph)H (1-H), CpFe((P2N2Ph)-N-Ph)H (2-H), CpFe((P2C5)-C-Ph)H (3-H)] and H-2 complexes [CpFe((P2N2Bn)-N-Ph)(H-2)]BAr4F, [1-H-2]BAr4F, (where BAr4F is B[(3,5-(CF3)(2)C6H3)(4)](-)), [CpFe((P2N2Ph)-N-Ph)(H-2)]BAr4F, [2-H-2]BAr4F, and [CpFe((P2C5)-C-Ph)(H-2)]-BAr4F, [3-H-2]BAr4F, as well as [CpFe((P2N2Bn)-N-Ph)(CO)]BAr4F, [1-CO]CI. Structural studies are reported for [1-H-2]BAr4F, 1-H, 2-H, and [1-CO]CI. The conformations adopted by the chelate rings of the (P2N2Bn)-N-Ph ligand in the different complexes are determined by attractive or repulsive interactions between the sixth ligand of these pseudo-octahedral complexes and the pendant N atom of the ring adjacent to the sixth ligand. An example of an attractive interaction is the observation that the distance between the N atom of the pendant amine and the C atom of the coordinated CO ligand for [1-CO]BAr4F is 2.848 angstrom, considerably shorter than the sum of the van der Waals radii of N and C atoms. Studies of H/D exchange by the complexes [1-H-2](+), [2-H-2](+), and [3-H-2](+) carried out using H-2 and D-2 indicate that the relatively rapid H/D exchange observed for [1-H-2](+) and [2-H-2](+) compared to [3-H-2](+) is consistent with intramolecular heterolytic cleavage of H-2 mediated by the pendant amine. Computational studies indicate a low barrier for heterolytic cleavage of H-2. These mononudear Fe-II dihydrogen complexes containing pendant amines in the ligands mimic crucial features of the distal Fe site of the active site of the [FeFe]-hydrogenase required for H-H bond formation and cleavage.

  DOI：

  10.1021/ja211193j