| 192228-97-0

• CAS: 192228-97-0
• 化学式: C₁₉H₁₇Cl₃N₃Re
• 分子量: 579.93
• InChiKey: XOVDFAYKXAKLDT-BSPLOEOUSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  、 硝酸 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Variable-Valent Re⋮NAr Species. A Family of Re^VINAr Amide Complexes and Their Re^VNAr Imine Precursors Related by Oxygen Atom Transfer

  摘要：

  Imide complexes of type (ReCl3)-Cl-V(X-SB)(NC6H4Y(p)), with X, Y = H, Me, OMe, Cl have been synthesized where X-SB is the Schiff base of pyridine-2-carboxaldehyde (the corresponding complex is 4), 2-acetylpyridine (5), 2-benzoylpyridine (6), and anilines, p-XC6H4NH2. Treatment of 4 or 5 (but not 6) with aqueous nitric acid in acetonitrile afforded (ReCl3)-Cl-VI(X-PA)(NC6H4Y(p)), 7, via oxygen atom transfer (X-PA = monoanionic picolinamide). In the structures of 5(X=Cl,Y=Cl), 6(OMe,OMe), and 7(Me,Me), the chlorine atoms are meridionally disposed in a ReCl3N3 coordination sphere. The trans influence of the imide nitrogen considerably lengthens the Re-N(pyridine) bond. The ReNC6H4Y(p) group has the triple-bonded linear moiety, Re equivalent to N-C. The amide group in 7(Me,Me) is planar. In 6(OMe,OMe) the two aryl rings on the imine function block water attack and hence amide formation. The rhenium(VI)-rhenium(V) E-1/2 values for 4-6 (0.7-1.0 V vs SCE) are much higher than that for 7 (E-1/2 similar to 0.15 V), which displays the rhenium(VII)-rhenium(VI) couple near 1.6 V. Six EPR hyperfine lines are observed for solutions of 7 at room temperature (g(iso) similar to 1.91; A(av) similar to 490 G). Crystal data for the complexes are as follows: 5(Cl,Cl), empirical formula C19H15Cl5N3Re, crystal system monoclinic, space group P2(1)/c, a = 13.360(6) Angstrom, b = 12.110(3) Angstrom, c = 14.954(9) Angstrom, beta = 111.41(4)degrees, V = 2252.4(1.7) Angstrom(3), Z = 4; 6(OMe,OMe), empirical formula C26H23Cl3N3O2Re, crystal system orthorhombic, space group Pbca, a = 12.079(5) Angstrom, b = 17.083(9) Angstrom, c = 26.049(9) Angstrom, V = 5375.4(4.0) Angstrom(3), Z = 8; 7(Me,Me), empirical formula C20H18Cl3N3ORe, crystal system monoclinic, space group P2(1)/c, a = 7.071(2) Angstrom, b = 17.541(6) Angstrom, c = 16.857(8) Angstrom, beta = 100.59(3)degrees, V = 2055.3(1.3) Angstrom(3), Z = 4.

  DOI：

  10.1021/ic9701322
• 作为产物：
  描述：

  2-乙酰基吡啶 、 [ReOCl₃(PPh₃)₂] 、 苯胺 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Variable-Valent Re⋮NAr Species. A Family of Re^VINAr Amide Complexes and Their Re^VNAr Imine Precursors Related by Oxygen Atom Transfer

  摘要：

  Imide complexes of type (ReCl3)-Cl-V(X-SB)(NC6H4Y(p)), with X, Y = H, Me, OMe, Cl have been synthesized where X-SB is the Schiff base of pyridine-2-carboxaldehyde (the corresponding complex is 4), 2-acetylpyridine (5), 2-benzoylpyridine (6), and anilines, p-XC6H4NH2. Treatment of 4 or 5 (but not 6) with aqueous nitric acid in acetonitrile afforded (ReCl3)-Cl-VI(X-PA)(NC6H4Y(p)), 7, via oxygen atom transfer (X-PA = monoanionic picolinamide). In the structures of 5(X=Cl,Y=Cl), 6(OMe,OMe), and 7(Me,Me), the chlorine atoms are meridionally disposed in a ReCl3N3 coordination sphere. The trans influence of the imide nitrogen considerably lengthens the Re-N(pyridine) bond. The ReNC6H4Y(p) group has the triple-bonded linear moiety, Re equivalent to N-C. The amide group in 7(Me,Me) is planar. In 6(OMe,OMe) the two aryl rings on the imine function block water attack and hence amide formation. The rhenium(VI)-rhenium(V) E-1/2 values for 4-6 (0.7-1.0 V vs SCE) are much higher than that for 7 (E-1/2 similar to 0.15 V), which displays the rhenium(VII)-rhenium(VI) couple near 1.6 V. Six EPR hyperfine lines are observed for solutions of 7 at room temperature (g(iso) similar to 1.91; A(av) similar to 490 G). Crystal data for the complexes are as follows: 5(Cl,Cl), empirical formula C19H15Cl5N3Re, crystal system monoclinic, space group P2(1)/c, a = 13.360(6) Angstrom, b = 12.110(3) Angstrom, c = 14.954(9) Angstrom, beta = 111.41(4)degrees, V = 2252.4(1.7) Angstrom(3), Z = 4; 6(OMe,OMe), empirical formula C26H23Cl3N3O2Re, crystal system orthorhombic, space group Pbca, a = 12.079(5) Angstrom, b = 17.083(9) Angstrom, c = 26.049(9) Angstrom, V = 5375.4(4.0) Angstrom(3), Z = 8; 7(Me,Me), empirical formula C20H18Cl3N3ORe, crystal system monoclinic, space group P2(1)/c, a = 7.071(2) Angstrom, b = 17.541(6) Angstrom, c = 16.857(8) Angstrom, beta = 100.59(3)degrees, V = 2055.3(1.3) Angstrom(3), Z = 4.

  DOI：

  10.1021/ic9701322