1,5-diphenyl-1,5-diphosphacyclooctane | 125707-15-5

• 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: 1,5-diphenyl-1,5-diphosphacyclooctane
• 英文别名: 1,5-Diphenyl-1,5-diphosphocane
• CAS: 125707-15-5；125707-14-4；143923-02-8
• 化学式: C₁₈H₂₂P₂
• 分子量: 300.32
• InChiKey: GDIQKZBJYRMXLR-UHFFFAOYSA-N

物化性质

• 沸点：
  443.8±25.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  二氯四吡啶铁(II) 、 1,5-diphenyl-1,5-diphosphacyclooctane 以 not given 为溶剂， 以0%的产率得到CpFe(1,5-diphenyl-1,5-diphosphacyclooctane)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
• 作为产物：
  描述：

  1,3-二氯丙烷 、 1,4-双(二苯基膦)丁烷 生成 1,5-diphenyl-1,5-diphosphacyclooctane
  参考文献：
  名称：

  Brooks, P.; Gallagher, M.J.; Sarroff, A., Phosphorus and Sulfur and the Related Elements, 1987, vol. 30, p. 389 - 392

  摘要：

  DOI：

文献信息

• Structures of palladium(II) and nickel(II) complexes of the mesocyclic diphosphine, cis-1,5-diphenyl-1,5-diphosphacyclooctane
  作者：Brian W. Arbuckle、W.Kenneth Musker

  DOI：10.1016/s0277-5387(00)80205-3

  日期：1991.1

  The preparation and X-ray crystal structures of a planar mono complex of cis-1,5-diphenyl-1,5-diphosphacyclooctane with palladium(II) chloride and a pentacoordinated bis complex with nickel(II) chloride are reported. Dichloro(1,5-diphenyl-1,5-diphosphacyclooctane)palladium(II) crystallizes in the monoclinic space group C2/c with cell constants a = 26.647(6), b = 7.884(1), c = 13,053(3) angstrom, beta = 98.15(2)-degrees and Z = 4 at T = 130 K. Chloro-bis(1,5-diphenyl-1,5-diphosphacyclooctane)nickel(II) chloride crystallizes in the monoclinic space group P2(1)/n with a = 18.178(7), b = 10.225(2), c = 20.959(7) angstrom, beta = 111.77(2)-degrees and Z = 4 at T = 130 K.
• BROOKS, PETER J.;GALLAGHER, MICHAEL J.;SARROFF, ADRIAN;BOWYER, MICHAEL, PHOSPH., SULFOR AND SILICON AND RELAT. ELEM., 44,(1989) N-4, C. 235-247
  作者：BROOKS, PETER J.、GALLAGHER, MICHAEL J.、SARROFF, ADRIAN、BOWYER, MICHAEL

  DOI：——

  日期：——
• Brooks, P.; Gallagher, M.J.; Sarroff, A., Phosphorus and Sulfur and the Related Elements, 1987, vol. 30, p. 389 - 392
  作者：Brooks, P.、Gallagher, M.J.、Sarroff, A.

  DOI：——

  日期：——
• Synthesis, Characterization, and Reactivity of Fe Complexes Containing Cyclic Diazadiphosphine Ligands: The Role of the Pendant Base in Heterolytic Cleavage of H₂
  作者：Tianbiao Liu、Shentan Chen、Molly J. O’Hagan、Mary Rakowski DuBois、R. Morris Bullock、Daniel L. DuBois

  DOI：10.1021/ja211193j

  日期：2012.4.11

  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.