铜(I)-丁酸铜(CH3CH2CH2COO),室温 | 50671-60-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: 铜(I)-丁酸铜(CH3CH2CH2COO),室温
• 英文名称: copper n-butyrate
• 英文别名: copper(I) butyrate；cuprous butyrate；copper butanoate；copper butyrate；Cu(I)-butyrat；butanoate;copper(1+)
• CAS: 50671-60-8
• 化学式: C₄H₇O₂*Cu
• 分子量: 150.644
• InChiKey: HMRDQEMTHMWRIK-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.47
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  40.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  铜(I)-丁酸铜(CH3CH2CH2COO),室温 、 三环己基膦 以 乙醚 、 正己烷 为溶剂， 以89%的产率得到
  参考文献：
  名称：

  Role of the Metal Center in the Homogeneous Catalytic Decarboxylation of Select Carboxylic Acids. Copper(I) and Zinc(II) Derivatives of Cyanoacetate

  摘要：

  The mechanism by which copper(I) influences the decarboxylation of cyanoacetic acid has been studied comprehensively by means of structural and kinetic investigations. The copper(I) complexes, [(R(3)P)(2)CuO2CCH2CN](1,2), have been synthesized from the reaction of copper(I) n-butyrate with 1 equiv of cyanoacetic acid and 2 equiv of phosphine. In the case of R = Ph, the complex is shown to be a dimer, both in solution and in the solid state, consisting of two copper(I) centers bridged by two cyanoacetate groups that are bound to copper through both the carboxylate functionality and the nitrogen. On the other hand, for the sterically encumbered phosphine (R = Cy), the complex (3) is found by X-ray crystallography to be monomeric and to contain a monodentate carboxylate group. The monodentate nature of the cyanoacetate binding was demonstrated to be a function of the electron-withdrawing ability of the cyanoacetate ligand as revealed by an examination of the solid-state structure of the (Cy(3)P)(2)Cu(butyrate) (4) analog, where the more basic butyrate ligand was shown to be bound in a bidentate manner. Both phosphine derivatives of copper(I) cyanoacetate were observed to readily undergo reversible decarboxylation/carboxylation processes as evidenced by their exchange reactions with (CO2)-C-13. A similar, much slower, exchange reaction with C-13-labeled CO2 was noted for the [PPN][O2CCH2CN] and eta(3)-HB(3-PhPz)(3)Zn(O2CCH2CN) (5) salts. These (CO2)-C-13 exchange processes were found to be first-order in the respective substrate, with the Cy(3)P derivative undergoing more rapid exchange than the Ph(3)P complex. Furthermore, the phosphine derivatives of copper(I) cyanoacetate were efficient catalysts for the decarboxylation of cyanoacetic acid to afford CH3CN and CO2 at rates quite similar to the CO2 exchange process. These reactions were first-order in copper(I) complexes and zero-order in cyanoacetic acid concentrations below 0.05 M. At higher acid concentrations the reaction was inhibited by cyanoacetic acid due to its complexation with copper(I). Both eta(3)-HB(3-PhPz)(3)Zn(O2CCH2CN) and [([12]ane(3))Zn(O2CCH3)][Ph(4)B] are effective catalysts as well for the decarboxylation of cyanoacetic acid, with the latter cationic derivative being more active. This difference in catalytic behavior is attributed to the weaker Zn-O bond in the cationic derivative as determined by X-ray crystallography, 1.941 vs 1.912 Angstrom. A mechanism for decarboxylation is proposed which involves CO2 elimination from a cyanoacetic ligand that is nitrile bound to the metal center, i.e., electrophilic catalysis. Crystal data for 3: monoclinic space group P2(1)/n, a = 10.619(2) Angstrom, b = 20.628(3) Angstrom, c = 18.146(3) Angstrom, beta = 93.89(1)degrees, Z = 2, R = 6.40%. Crystal data for 4: triclinic space group P1, a = 9.706(2) Angstrom, b = 10.442(2) Angstrom, c = 22.423(4) Angstrom, alpha = 97.51(2)degrees, beta 92.30(2)degrees, gamma = 116.22(1)degrees, Z = 2, R = 4.91%. Crystal data for 5: triclinic space group P1, a = 13.197(2) Angstrom, b = 14.657(2) Angstrom, c = 16.049(3) Angstrom, alpha = 103.44(1)degrees, beta = 107.10(1)degrees, gamma = 92.19(1)degrees, Z = 2, R = 4.72%.

  DOI：

  10.1021/ja00106a034
• 作为产物：
  描述：

  copper(II) butyrate 以 neat (no solvent) 为溶剂， 生成 铜(I)-丁酸铜(CH3CH2CH2COO),室温 、 丁酸
  参考文献：
  名称：

  Il'ina, E. G.; Santalova, N. A.; Dunaeva, K. M., Russian Journal of Inorganic Chemistry, 1991, vol. 36, p. 1297 - 1299

  摘要：

  DOI：

文献信息

• Darensbourg, Donald J.; Holtcamp, Matthew W.; Khandelwal, Bandana, Inorganic Chemistry, 1995, vol. 34, # 9, p. 2389 - 2398
  作者：Darensbourg, Donald J.、Holtcamp, Matthew W.、Khandelwal, Bandana、Klausmeyer, Kevin K.、Reibenspies, Joseph H.

  DOI：——

  日期：——
• Darensbourg, Donald J.; Longridge, Elisabeth M.; Holtcamp, Matthew W., Journal of the American Chemical Society, 1993, vol. 115, p. 8839 - 8840
  作者：Darensbourg, Donald J.、Longridge, Elisabeth M.、Holtcamp, Matthew W.、Klausmeyer, Kevin K.、Reibenspies, Joseph H.

  DOI：——

  日期：——
• Darensbourg, Donald J.; Holtcamp, Matthew W.; Khandelwal, Bandana, Inorganic Chemistry, 1994, vol. 33, # 3, p. 531 - 537
  作者：Darensbourg, Donald J.、Holtcamp, Matthew W.、Khandelwal, Bandana、Reibenspies, Joseph H.

  DOI：——

  日期：——
• Role of the Metal Center in the Homogeneous Catalytic Decarboxylation of Select Carboxylic Acids. Copper(I) and Zinc(II) Derivatives of Cyanoacetate
  作者：Donald J. Darensbourg、Matthew W. Holtcamp、Elisabeth M. Longridge、Bandana Khandelwal、Kevin K. Klausmeyer、Joseph H. Reibenspies

  DOI：10.1021/ja00106a034

  日期：1995.1

  The mechanism by which copper(I) influences the decarboxylation of cyanoacetic acid has been studied comprehensively by means of structural and kinetic investigations. The copper(I) complexes, [(R(3)P)(2)CuO2CCH2CN](1,2), have been synthesized from the reaction of copper(I) n-butyrate with 1 equiv of cyanoacetic acid and 2 equiv of phosphine. In the case of R = Ph, the complex is shown to be a dimer, both in solution and in the solid state, consisting of two copper(I) centers bridged by two cyanoacetate groups that are bound to copper through both the carboxylate functionality and the nitrogen. On the other hand, for the sterically encumbered phosphine (R = Cy), the complex (3) is found by X-ray crystallography to be monomeric and to contain a monodentate carboxylate group. The monodentate nature of the cyanoacetate binding was demonstrated to be a function of the electron-withdrawing ability of the cyanoacetate ligand as revealed by an examination of the solid-state structure of the (Cy(3)P)(2)Cu(butyrate) (4) analog, where the more basic butyrate ligand was shown to be bound in a bidentate manner. Both phosphine derivatives of copper(I) cyanoacetate were observed to readily undergo reversible decarboxylation/carboxylation processes as evidenced by their exchange reactions with (CO2)-C-13. A similar, much slower, exchange reaction with C-13-labeled CO2 was noted for the [PPN][O2CCH2CN] and eta(3)-HB(3-PhPz)(3)Zn(O2CCH2CN) (5) salts. These (CO2)-C-13 exchange processes were found to be first-order in the respective substrate, with the Cy(3)P derivative undergoing more rapid exchange than the Ph(3)P complex. Furthermore, the phosphine derivatives of copper(I) cyanoacetate were efficient catalysts for the decarboxylation of cyanoacetic acid to afford CH3CN and CO2 at rates quite similar to the CO2 exchange process. These reactions were first-order in copper(I) complexes and zero-order in cyanoacetic acid concentrations below 0.05 M. At higher acid concentrations the reaction was inhibited by cyanoacetic acid due to its complexation with copper(I). Both eta(3)-HB(3-PhPz)(3)Zn(O2CCH2CN) and [([12]ane(3))Zn(O2CCH3)][Ph(4)B] are effective catalysts as well for the decarboxylation of cyanoacetic acid, with the latter cationic derivative being more active. This difference in catalytic behavior is attributed to the weaker Zn-O bond in the cationic derivative as determined by X-ray crystallography, 1.941 vs 1.912 Angstrom. A mechanism for decarboxylation is proposed which involves CO2 elimination from a cyanoacetic ligand that is nitrile bound to the metal center, i.e., electrophilic catalysis. Crystal data for 3: monoclinic space group P2(1)/n, a = 10.619(2) Angstrom, b = 20.628(3) Angstrom, c = 18.146(3) Angstrom, beta = 93.89(1)degrees, Z = 2, R = 6.40%. Crystal data for 4: triclinic space group P1, a = 9.706(2) Angstrom, b = 10.442(2) Angstrom, c = 22.423(4) Angstrom, alpha = 97.51(2)degrees, beta 92.30(2)degrees, gamma = 116.22(1)degrees, Z = 2, R = 4.91%. Crystal data for 5: triclinic space group P1, a = 13.197(2) Angstrom, b = 14.657(2) Angstrom, c = 16.049(3) Angstrom, alpha = 103.44(1)degrees, beta = 107.10(1)degrees, gamma = 92.19(1)degrees, Z = 2, R = 4.72%.
• Il'ina, E. G.; Santalova, N. A.; Dunaeva, K. M., Russian Journal of Inorganic Chemistry, 1991, vol. 36, p. 1297 - 1299
  作者：Il'ina, E. G.、Santalova, N. A.、Dunaeva, K. M.

  DOI：——

  日期：——