2,2,7,7,12,12,17,17-Octamethyl-24-phenyl-26-thia-25,27-diaza-24-phosphahexacyclo[16.5.1.13,6.18,11.113,16.019,23]heptacosa-1(23),3,5,8,10,13,15,18-octaene | 897672-56-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: 2,2,7,7,12,12,17,17-Octamethyl-24-phenyl-26-thia-25,27-diaza-24-phosphahexacyclo[16.5.1.13,6.18,11.113,16.019,23]heptacosa-1(23),3,5,8,10,13,15,18-octaene
• 英文别名: 2,2,7,7,12,12,17,17-octamethyl-24-phenyl-26-thia-25,27-diaza-24-phosphahexacyclo[16.5.1.13,6.18,11.113,16.019,23]heptacosa-1(23),3,5,8,10,13,15,18-octaene
• CAS: 897672-56-9
• 化学式: C₃₇H₄₃N₂PS
• 分子量: 578.802
• InChiKey: LIQGKIGIHIIRKA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  41
• 可旋转键数：
  1
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  59.8
• 氢给体数：
  2
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,2,7,7,12,12,17,17-Octamethyl-24-phenyl-26-thia-25,27-diaza-24-phosphahexacyclo[16.5.1.13,6.18,11.113,16.019,23]heptacosa-1(23),3,5,8,10,13,15,18-octaene 、 palladium dichloride 以 甲苯 为溶剂， 以88%的产率得到
  参考文献：
  名称：

  Synthesis, Structures, and Coordinating Properties of Phosphole-Containing Hybrid Calixpyrroles

  摘要：

  Symmetric and asymmetric hybrid calixpyrroles containing a sigma(4)-phosphole or sigma(4)-2,3-dihydrophosphole unit (symmetric and asymmetric sigma(4)-P,N-2,X-hybrids: X = S, O) were prepared by using acid-promoted condensation reactions of the corresponding sigma(4)-phosphatripyrranes with 2,5-bis(1-hydroxy-1-methylethyl)heteroles. The X-ray crystallographic analyses of the symmetric and asymmetric sigma(4)-P,N-2,X-hybrids show that the cavity sizes of the sigma-P,N-2,S-hybrids are larger than those of the sigma(4)-P,N-2,O-hybrids, mainly reflecting the difference in edge-to-edge distances of the thiophene and furan rings. The symmetric sigma(4)-P,N-2,X-hybrids and the asymmetric sigma(4)-P,N-2,S-hybrid were successfully converted to the corresponding sigma(3) forms by reductive desulfurization at the phosphorus center. Each of the symmetric sigma(3)-P,N-2,X-hybrids was obtained as a mixture of two conformers, where the lone pair of the phosphorus atom is located inside (in) and outside (out) the cavity. The interconversion between the in and out type conformers of the asymmetric sigma(3)-P,N-2,S-hybrid was sufficiently slow to isolate each of them. The complexation reactions of the symmetric sigma(3)-P,N-2,S-hybrid with Au(I), Pt(II), and Pd(II) ions afforded both of the in and out type complexes, where the in type complexes were the thermodynamically favored products. In the complexation reactions of the asymmetric sigma(3)-P,N-2, S-hybrids, the stereochemistry at the phosphorus center was retained to give the in or out type complex exclusively. In the in-in type trans-M(II)-bis(phosphine) complexes (M = Pt, Pd) derived from the symmetric and asymmetric sigma(3)-P,N-2,S-hybrids, the M-Cl fragment is bound above the cavities of the two macrocycles. The crystal structures and the H-1 NMR spectra of these M(II) complexes reveal that the P,N-2,S-hybrid calixpyrroles bind the M-Cl fragments through P-M coordination and cooperative NH-Cl hydrogen-bonding interactions.

  DOI：

  10.1021/om800099h

文献信息

• Phosphole-Containing Hybrid Calixpyrroles:  New Multifunctional Macrocyclic Ligands for Platinum(II) Ions
  作者：Yoshihiro Matano、Takashi Nakabuchi、Tooru Miyajima、Hiroshi Imahori

  DOI：10.1021/om060300a

  日期：2006.6.1

  Phosphole-containing hybrid calixpyrroles have been prepared by acid-promoted condensation reactions. σ3-Calix[1]phosphole[1]thiophene[2]pyrrole reacts with PtCl2(COD) to afford an unusual type of macrocyclic Pt(II)−monophosphine complex bearing a η3-cyclooctadienyl ligand, in which the phosphole and pyrrole units bind the Pt−Cl moiety through cooperative, noncovalent bonding interactions.

  含磷杂杂杯吡咯已经通过酸促进的缩合反应制备。σ 3 -Calix [1]磷杂[1]噻吩[2]吡咯起反应以氯铂酸2（COD），得到寻常型大环的Pt（II）络合物-monophosphine轴承一个η 3 -cyclooctadienyl配体，其中，所述磷杂环和吡咯单元通过协同的非共价键相互作用与Pt-Cl部分结合。
• Synthesis, Structures, and Coordinating Properties of Phosphole-Containing Hybrid Calixpyrroles
  作者：Takashi Nakabuchi、Yoshihiro Matano、Hiroshi Imahori

  DOI：10.1021/om800099h

  日期：2008.7.1

  Symmetric and asymmetric hybrid calixpyrroles containing a sigma(4)-phosphole or sigma(4)-2,3-dihydrophosphole unit (symmetric and asymmetric sigma(4)-P,N-2,X-hybrids: X = S, O) were prepared by using acid-promoted condensation reactions of the corresponding sigma(4)-phosphatripyrranes with 2,5-bis(1-hydroxy-1-methylethyl)heteroles. The X-ray crystallographic analyses of the symmetric and asymmetric sigma(4)-P,N-2,X-hybrids show that the cavity sizes of the sigma-P,N-2,S-hybrids are larger than those of the sigma(4)-P,N-2,O-hybrids, mainly reflecting the difference in edge-to-edge distances of the thiophene and furan rings. The symmetric sigma(4)-P,N-2,X-hybrids and the asymmetric sigma(4)-P,N-2,S-hybrid were successfully converted to the corresponding sigma(3) forms by reductive desulfurization at the phosphorus center. Each of the symmetric sigma(3)-P,N-2,X-hybrids was obtained as a mixture of two conformers, where the lone pair of the phosphorus atom is located inside (in) and outside (out) the cavity. The interconversion between the in and out type conformers of the asymmetric sigma(3)-P,N-2,S-hybrid was sufficiently slow to isolate each of them. The complexation reactions of the symmetric sigma(3)-P,N-2,S-hybrid with Au(I), Pt(II), and Pd(II) ions afforded both of the in and out type complexes, where the in type complexes were the thermodynamically favored products. In the complexation reactions of the asymmetric sigma(3)-P,N-2, S-hybrids, the stereochemistry at the phosphorus center was retained to give the in or out type complex exclusively. In the in-in type trans-M(II)-bis(phosphine) complexes (M = Pt, Pd) derived from the symmetric and asymmetric sigma(3)-P,N-2,S-hybrids, the M-Cl fragment is bound above the cavities of the two macrocycles. The crystal structures and the H-1 NMR spectra of these M(II) complexes reveal that the P,N-2,S-hybrid calixpyrroles bind the M-Cl fragments through P-M coordination and cooperative NH-Cl hydrogen-bonding interactions.