tris(4-phenylphosphinato-3-methyl-3-azabutyl)amine trihydrochloride monohydrate | 777833-09-7

• 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: tris(4-phenylphosphinato-3-methyl-3-azabutyl)amine trihydrochloride monohydrate
• 英文别名: tris(4-(phenylphosphinato)-3-methyl-3-azabutyl)amine；[2-[Bis[2-[methyl-[[oxido(phenyl)phosphoryl]methyl]azaniumyl]ethyl]amino]ethyl-methylazaniumyl]methyl-phenylphosphinate
• CAS: 777833-09-7
• 化学式: C₃₀H₄₅N₄O₆P₃
• 分子量: 650.632
• InChiKey: NBWMKUJMRFFOFK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -5.5
• 重原子数：
  43
• 可旋转键数：
  18
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  125
• 氢给体数：
  3
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  氯化钬 、 tris(4-phenylphosphinato-3-methyl-3-azabutyl)amine trihydrochloride monohydrate 以 水 为溶剂， 以43%的产率得到[Ho(tris(4-phenylphosphinato-3-methyl-3-azabutyl)amine)2]Cl3*5H2O*2HCl
  参考文献：
  名称：

  Tightening the Hydrophobic Belt:  Effects of Backbone and Donor Group Variation on Podand Ligand Complexes of the Lanthanides

  摘要：

  The N4O3 tripodal aminomethylene phosphinato ligand tris(4-phenylphosphinato-3-methyl-3-azabutyl)amine (H-3-ppma) forms mono- and bis(ligand) complexes with lanthanide(III) metal ions Ln when Ln = Sm-Lu. The formation constants of the Lu (log beta(1) = 1.79, log beta(2) = 4.40) and the Yb (log beta(1) = 2.25, log beta(2) = 4.42) complexes were determined at pH = 1.5 using an unusual P-31 NMR spectroscopic method. The molecular structure of the lutetium complex [Lu(H(3)ppma)(2)](NO3)(3) . 3H(2)O (C60H96LuN11O24P6) was solved by X-ray methods; it crystallizes in the trigonal space group R(3) over barc$, with a = 19.060(1) Angstrom, c = 36.395(3) Angstrom, and Z = 6. The structure was solved by Patterson methods and was refined by full-matrix least-squares procedures to R = 0.024 (R-W = 0.025) for 2061 reflections with I > 3(l). The ligand coordinates in a tridentate manner through the three phosphinate oxygens, resulting in a bicapped octahedral structure of exact Sg symmetry, which is preserved in solution as shown by H-1 and P-31 NMR spectroscopies (CD3OD, DMSO-d(6)). The two N3O3 tripodal amine phenol ligands 1,1,1-tris(((2-hydroxy-5-sulfobenzyl)amino)methyl)ethane (H(6)tams) and 1,2,3-tris((2-hydroxy-5-sulfobenzyl)amino)propane (H(6)taps) showed a binding modality different from that with H(3)ppma, forming N3O3 encapsulated complexes whereby all six donor atoms bind to the lanthanide. This complexation was investigated potentiometrically at 25 degrees C and 0.16 M NaCl. log K values of [M(tams)](3-) ([M(Htams)](2-)) for M: La, 9.17; Nd, 11.19; Gd, 11.86 (18.41); Ho, 12.71 (19.40); Yb, 13.78 (20.11). log K values of [M(taps)](3-) ([M(Htaps)](2-)) for M: La, 11.33 (18.47); Nd, 13.59 (20.13); Gd, 14.50 (20.88); Ho, 14.71 (21.15); Yb, 15.15 (21.54). The formation constants show an increasing affinity for the heavier lanthanides, with H(6)taps forming the more stable complexes. O-17 NMR spectroscopy of [Dy(tams)](3-) and [Dy(taps)](3-) indicated the presence of three inner-sphere water molecules, implying a 9-coordinate Dy in each complex. The factors governing the coordination geometries in the solid and solution states and chelation of these and related metal ion complexes are discussed with reference to the hydrophobic belt.

  DOI：

  10.1021/ic971488g
• 作为产物：
  描述：

  聚合甲醛 、 苯膦酸 、 三[2-(甲基氨基)乙基]胺 在 盐酸 作用下， 反应 5.0h， 以64%的产率得到tris(4-phenylphosphinato-3-methyl-3-azabutyl)amine trihydrochloride monohydrate
  参考文献：
  名称：

  Highly Symmetric Group 13 Metal−Phosphinato Complexes:  Multinuclear NMR (²⁷Al, ³¹P, ⁷¹Ga) Determination of Stability Constants at Low pH

  摘要：

  An N4O3 tripodal tren-based (aminomethylene)phosphinato ligand tris(4-(phenylphosphinato)-3-methyl-3-azabutyl)amine (H(3)ppma) has been synthesized, and its complexation properties with the group 13 metals Al, Ga. and In have been investigated. The molecular structure of the indium complex [In(H(3)ppma)(2)](NO3)(3) . 3H(2)O (C60H96InN11O24P6) has been solved by X-ray methods; the complex crystallizes in the trigonal space group R(3) over barc$, with a = 18.984(3) Angstrom, c = 36.256(5) Angstrom, and Z = 6, The structure was solved by Patterson methods and was refined by full-matrix least-squares procedures to R = 0.040 (R(w) = 0.039) for 1415 reflections with I > 3 sigma(I). The structure of the bis-complex showed the ligand to coordinate in a tridentate manner through the three phosphinate oxygens, resulting in a bicapped octahedral structure of exact S-6 symmetry. The solved structure was of the RRRSSS diastereomer, where half of the molecule contained phosphorus atoms of R chirality and the other half contained phosphorus atoms of S chirality. The highly symmetric environment about the metal atoms produces a low electric field gradient at the metal nucleus leading to unusually narrow line widths in the Al-27, Ga-71, and In-115 NMR spectra. The aluminum complex [Al(II(3)ppma)(2)](NO3)(3) . 2H(2)O exhibited an extremely rare example of aluminum-phosphorus coupling in both the P-31 and Al-27 NMR spectra, where (2)J(AIP) was shown from both spectra to be 6.7 Hz. The narrow line widths made the complexes amenable to stability constant studies via a combination of Al-27, Ga-71, and P-31 NMR spectroscopies (25 degrees C), The formation constants for In3+ (log beta(2) greater than or equal to 5.4), Ga3+ (log beta(2) greater than or equal to 4.24), and Al3+ (log beta(1) = 0.93, log beta(2) = 3.45) decrease by an order oi magnitude as the group is ascended, consistent with increasing steric interactions of the phenyl groups as the two phosphosphinate ligands are crowded together in order to coordinate the smaller metal ions. Variable temperature Al-27 and P-31 NMR spectroscopic studies indicated the RRRSSS diastereomer to be rigid up to 55 degrees C in CD3OD.

  DOI：

  10.1021/ja961633+

文献信息

• US6060614A
  申请人：——

  公开号：US6060614A

  公开（公告）日：2000-05-09
• [EN] NOVEL CHELATING LIGANDS HAVING A TRIPODAL BACKBONE<br/>[FR] NOUVEAUX LIGANDS CHELATEURS COMPRENANT UNE SQUELETTE A TROIS BRANCHES
  申请人：THE UNIVERSITY OF BRITISH COLUMBIA

  公开号：WO1999002538A1

  公开（公告）日：1999-01-21

  (EN) The invention relates to novel chelating ligands which incorporate a tripodal backbone. More particularly, the invention pertains to novel tripodal ligands which form coordination compounds with a variety of metal ions, particularly, but not exclusively, trivalent metal ions and lanthanide metal ions, which are useful in nuclear medicine. A novel amine phosphinate tripodal ligand, a chelating ligand and a process therefor involving a metal ion and particularly a trivalent metal ion of the group 13 metals and the rare earths. The process comprises complexing Tc or Re or any one of the group 13 metals, Al, Ga and In, and any one of the rare earths, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, En, Tm, Yb and Lu, with an amine phosphinate tripodal ligand.(FR) L'invention concerne de nouveaux ligands chélateurs comprenant un squelette à trois branches. De manière plus spécifique cette invention concerne de nouveaux ligands à trois branches qui forment des composés de coordination avec une variété d'ions métal, particulièrement mais sans exclusive avec des ions métal trivalents et des ions métal lanthanides qui sont utiles en médecine nucléaire. On décrit un nouveau ligand à trois branches d'amine phosphinate, un ligand chélateur et un procédé associé comprenant un ion métal et plus particulièrement un ion métal trivalent des métaux du groupe 13 et des métaux des terres rares. Le procédé consiste à former un complexe Tc ou Re ou bien un complexe de n'importe lequel des métaux du groupe 13, Al, Ga et In, et de n'importe lequel des métaux des terres rares, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, En, Tm, Yb et Lu avec un ligand à trois branches d'amine phosphinate.
• Highly Symmetric Group 13 Metal−Phosphinato Complexes:  Multinuclear NMR (²⁷Al, ³¹P, ⁷¹Ga) Determination of Stability Constants at Low pH
  作者：Mark P. Lowe、Steven J. Rettig、Chris Orvig

  DOI：10.1021/ja961633+

  日期：1996.1.1

  An N4O3 tripodal tren-based (aminomethylene)phosphinato ligand tris(4-(phenylphosphinato)-3-methyl-3-azabutyl)amine (H(3)ppma) has been synthesized, and its complexation properties with the group 13 metals Al, Ga. and In have been investigated. The molecular structure of the indium complex [In(H(3)ppma)(2)](NO3)(3) . 3H(2)O (C60H96InN11O24P6) has been solved by X-ray methods; the complex crystallizes in the trigonal space group R(3) over barc$, with a = 18.984(3) Angstrom, c = 36.256(5) Angstrom, and Z = 6, The structure was solved by Patterson methods and was refined by full-matrix least-squares procedures to R = 0.040 (R(w) = 0.039) for 1415 reflections with I > 3 sigma(I). The structure of the bis-complex showed the ligand to coordinate in a tridentate manner through the three phosphinate oxygens, resulting in a bicapped octahedral structure of exact S-6 symmetry. The solved structure was of the RRRSSS diastereomer, where half of the molecule contained phosphorus atoms of R chirality and the other half contained phosphorus atoms of S chirality. The highly symmetric environment about the metal atoms produces a low electric field gradient at the metal nucleus leading to unusually narrow line widths in the Al-27, Ga-71, and In-115 NMR spectra. The aluminum complex [Al(II(3)ppma)(2)](NO3)(3) . 2H(2)O exhibited an extremely rare example of aluminum-phosphorus coupling in both the P-31 and Al-27 NMR spectra, where (2)J(AIP) was shown from both spectra to be 6.7 Hz. The narrow line widths made the complexes amenable to stability constant studies via a combination of Al-27, Ga-71, and P-31 NMR spectroscopies (25 degrees C), The formation constants for In3+ (log beta(2) greater than or equal to 5.4), Ga3+ (log beta(2) greater than or equal to 4.24), and Al3+ (log beta(1) = 0.93, log beta(2) = 3.45) decrease by an order oi magnitude as the group is ascended, consistent with increasing steric interactions of the phenyl groups as the two phosphosphinate ligands are crowded together in order to coordinate the smaller metal ions. Variable temperature Al-27 and P-31 NMR spectroscopic studies indicated the RRRSSS diastereomer to be rigid up to 55 degrees C in CD3OD.
• Tightening the Hydrophobic Belt:  Effects of Backbone and Donor Group Variation on Podand Ligand Complexes of the Lanthanides
  作者：Mark P. Lowe、P. Caravan、Steven J. Rettig、Chris Orvig

  DOI：10.1021/ic971488g

  日期：1998.4.1

  The N4O3 tripodal aminomethylene phosphinato ligand tris(4-phenylphosphinato-3-methyl-3-azabutyl)amine (H-3-ppma) forms mono- and bis(ligand) complexes with lanthanide(III) metal ions Ln when Ln = Sm-Lu. The formation constants of the Lu (log beta(1) = 1.79, log beta(2) = 4.40) and the Yb (log beta(1) = 2.25, log beta(2) = 4.42) complexes were determined at pH = 1.5 using an unusual P-31 NMR spectroscopic method. The molecular structure of the lutetium complex [Lu(H(3)ppma)(2)](NO3)(3) . 3H(2)O (C60H96LuN11O24P6) was solved by X-ray methods; it crystallizes in the trigonal space group R(3) over barc$, with a = 19.060(1) Angstrom, c = 36.395(3) Angstrom, and Z = 6. The structure was solved by Patterson methods and was refined by full-matrix least-squares procedures to R = 0.024 (R-W = 0.025) for 2061 reflections with I > 3(l). The ligand coordinates in a tridentate manner through the three phosphinate oxygens, resulting in a bicapped octahedral structure of exact Sg symmetry, which is preserved in solution as shown by H-1 and P-31 NMR spectroscopies (CD3OD, DMSO-d(6)). The two N3O3 tripodal amine phenol ligands 1,1,1-tris(((2-hydroxy-5-sulfobenzyl)amino)methyl)ethane (H(6)tams) and 1,2,3-tris((2-hydroxy-5-sulfobenzyl)amino)propane (H(6)taps) showed a binding modality different from that with H(3)ppma, forming N3O3 encapsulated complexes whereby all six donor atoms bind to the lanthanide. This complexation was investigated potentiometrically at 25 degrees C and 0.16 M NaCl. log K values of [M(tams)](3-) ([M(Htams)](2-)) for M: La, 9.17; Nd, 11.19; Gd, 11.86 (18.41); Ho, 12.71 (19.40); Yb, 13.78 (20.11). log K values of [M(taps)](3-) ([M(Htaps)](2-)) for M: La, 11.33 (18.47); Nd, 13.59 (20.13); Gd, 14.50 (20.88); Ho, 14.71 (21.15); Yb, 15.15 (21.54). The formation constants show an increasing affinity for the heavier lanthanides, with H(6)taps forming the more stable complexes. O-17 NMR spectroscopy of [Dy(tams)](3-) and [Dy(taps)](3-) indicated the presence of three inner-sphere water molecules, implying a 9-coordinate Dy in each complex. The factors governing the coordination geometries in the solid and solution states and chelation of these and related metal ion complexes are discussed with reference to the hydrophobic belt.