[Cu(5,5'-bis(BMes2)-2,2'-bipy)(PPh3)2][BF4] | 944393-88-8

• 英文名称: [Cu(5,5'-bis(BMes2)-2,2'-bipy)(PPh3)2][BF4]
• CAS: 944393-88-8
• 化学式: BF₄*C₈₂H₈₀B₂CuN₂P₂
• 分子量: 1327.47
• InChiKey: NJJNAGWVABGYEA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
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• 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：

  [Cu(5,5'-bis(BMes2)-2,2'-bipy)(PPh3)2][BF4] 、 四丁基氟化铵 以 甲醇 、 二氯甲烷 为溶剂， 以99%的产率得到Cu(5,5'-bis(BMes₂)-2,2'-bipyF)(PPh₃)2
  参考文献：
  名称：

  Enhancing Electron Accepting Ability of Triarylboron via π-Conjugation with 2,2‘-Bipy and Metal Chelation:  5,5‘-Bis(BMes₂)-2,2‘-bipy and Its Metal Complexes

  摘要：

  The synthesis of a new diboron compound, 5,5'-bis(BMes(2))-2,2'-bipy (B2bipy, 1), has been accomplished. The conjugation of the 2,2'-bipy unit with the two BMes(2) groups in 1 has been found to greatly enhance the electron-accepting ability of the boron centers, compared to the biphenyl analogue. 1 is an effective chelate ligand for metal ions and three metal complexes; namely, [Cu-I(B2bipy)(PPh3)(2)][BF4], 2, Pt-II(B2bipy)Ph-2, 3a, and Pt-II(B2bipy)Me-2, 3b, have been synthesized. The binding of metal ions to B2bipy was found to further significantly increase the electron-accepting ability/Lewis acidity of the boron centers. Cyclic voltammetry diagrams revealed that the free ligand and all three complexes display two reversible reduction peaks that are separated by 0.31-0.40 V. The first reduction potential (E-1/2) for 1, 2, 3a, and 3b was found to be -1.69, -1.36, -1.34, and -1.38 V, respectively, versus FeCp2+/0 in DMF, which supports that the electron-accepting ability of the metal complexes is much greater than that of BMes(C6F5)(2). The strong electron-accepting ability/Lewis acidity of the metal complexes and the free ligand was manifested by their ability to sequentially bind to 2 equiv of F- ions in non-alcoholic solvents with K-1 >= 10(8) and 10(9) M-1 for 1 and 3a, respectively, and to 1 equiv of F- ions in the presence of methanol/ethanol or water. The crystal structures of 1, its 2:1 fluoride adduct [NBu4](2)[1F(2)], and 3a were established by X-ray diffraction analyses. The 1:1 fluoride adduct of 2, [Cu-I(B2bipyF)(PPh3)(2)], 2F, isolated directly from the reaction of 2 with NBu4F in a 4:1 mixture of CH3OH and CH2Cl2 was characterized. All metal complexes are intensely colored and display a characteristic metal-to-ligand (B2bipy) charge transfer absorption band in the visible region, which was found to be highly sensitive toward binding by anions such as fluorides.

  DOI：

  10.1021/ja0725652
• 作为产物：
  描述：

  5,5'-bis-(dimesitylboranyl)-2,2'-bipyridine 、 [copper(I)(acetonitrile)2(PPh3)2](BF4) 以 not given 为溶剂， 生成 [Cu(5,5'-bis(BMes2)-2,2'-bipy)(PPh3)2][BF4]
  参考文献：
  名称：

  Enhancing Electron Accepting Ability of Triarylboron via π-Conjugation with 2,2‘-Bipy and Metal Chelation:  5,5‘-Bis(BMes₂)-2,2‘-bipy and Its Metal Complexes

  摘要：

  The synthesis of a new diboron compound, 5,5'-bis(BMes(2))-2,2'-bipy (B2bipy, 1), has been accomplished. The conjugation of the 2,2'-bipy unit with the two BMes(2) groups in 1 has been found to greatly enhance the electron-accepting ability of the boron centers, compared to the biphenyl analogue. 1 is an effective chelate ligand for metal ions and three metal complexes; namely, [Cu-I(B2bipy)(PPh3)(2)][BF4], 2, Pt-II(B2bipy)Ph-2, 3a, and Pt-II(B2bipy)Me-2, 3b, have been synthesized. The binding of metal ions to B2bipy was found to further significantly increase the electron-accepting ability/Lewis acidity of the boron centers. Cyclic voltammetry diagrams revealed that the free ligand and all three complexes display two reversible reduction peaks that are separated by 0.31-0.40 V. The first reduction potential (E-1/2) for 1, 2, 3a, and 3b was found to be -1.69, -1.36, -1.34, and -1.38 V, respectively, versus FeCp2+/0 in DMF, which supports that the electron-accepting ability of the metal complexes is much greater than that of BMes(C6F5)(2). The strong electron-accepting ability/Lewis acidity of the metal complexes and the free ligand was manifested by their ability to sequentially bind to 2 equiv of F- ions in non-alcoholic solvents with K-1 >= 10(8) and 10(9) M-1 for 1 and 3a, respectively, and to 1 equiv of F- ions in the presence of methanol/ethanol or water. The crystal structures of 1, its 2:1 fluoride adduct [NBu4](2)[1F(2)], and 3a were established by X-ray diffraction analyses. The 1:1 fluoride adduct of 2, [Cu-I(B2bipyF)(PPh3)(2)], 2F, isolated directly from the reaction of 2 with NBu4F in a 4:1 mixture of CH3OH and CH2Cl2 was characterized. All metal complexes are intensely colored and display a characteristic metal-to-ligand (B2bipy) charge transfer absorption band in the visible region, which was found to be highly sensitive toward binding by anions such as fluorides.

  DOI：

  10.1021/ja0725652