1,1'''-bis(o-bromobenzoyl)biferrocene | 138208-53-4

• 英文名称: 1,1'''-bis(o-bromobenzoyl)biferrocene
• CAS: 138208-53-4
• 化学式: C₃₄H₂₄Br₂Fe₂O₂
• 分子量: 736.065
• InChiKey: CJIDUJUTLXQTJU-UHFFFAOYSA-N

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：

  1,1'''-bis(o-bromobenzoyl)biferrocene 在 LiAlH₄ 、 AlCl₃ 作用下， 以 乙醚 为溶剂， 以90%的产率得到1,1'''-bis(o-bromobenzyl)biferrocene
  参考文献：
  名称：

  取代基对混合价三碘化三碘化亚铁络合物中分子内电子转移速率的显著作用

  摘要：

  The factors controlling the rate of intramolecular electron transfer in the solid state have been studied for a series of binuclear mixed-valence 1',1'''-bis(substituted benzyl)biferrocenium triiodide salts, where the substituents in the benzyl unit are p-iodo (1), p-bromo (2), p-chloro (3), o-iodo (4), and o-bromo (5). The X-ray structure of neutral 1',1'''-bis(p-bromobenzyl)biferrocene has been determined at 298 K: P1BAR, a = 5.853 (4) angstrom, b = 8.380 (3) angstrom, c = 14.2295 (18) angstrom, alpha = 74.622 (15)-degrees, beta = 83.940 (23)-degrees, and gamma = 86.69 (4)-degrees; Z = 1, D(calcd) = 1.758 g cm-8, R(F) = 0.036, and R(wF) = 0.038. The Fe-Fe distance is 5.119 (3) angstrom. Compound 2 crystallizes in the triclinic space group P1BAR with one molecule in a unit cell with dimensions a = 9.5505 (24) angstrom, b = 10.984 (3) angstrom, c = 11.248 (5) angstrom, alpha = 119.71 (3)-degrees, beta = 116.04 (3)-degrees, and gamma = 76.946 (22)-degrees. The final discrepancy factors are R(F) = 0.052 and R(wF) = 0.039. A decrease in Fe-Fe distance (5.058 (7) angstrom) has been observed when 1',1'''-bis(p-bromobenzyl)biferrocene is oxidized. The solid-state structure of 2 is composed of parallel sheets of cations and polyiodide ions which contain zigzag chains of alternate I3- and I2 units. The distance of 3.487 (2) angstrom between neighboring iodine atoms in I2 and I3- units within a chain indicates a nonnegligible interaction. Compound 4 crystallizes in the triclinic space group P1BAR with one molecule in a unit cell with dimensions a = 8.149 (4) angstrom, b = 9.567 (3) angstrom, c = 12.491 (4) angstrom, alpha = 111.78 (3)-degrees, beta = 85.97 (4)-degrees, and gamma = 108.39 (3)-degrees. The final discrepancy factors for 4 and R(F) = 0.056 and R(wF) = 0.04. The Fe-Fe distance in 4 is 5.082 (8) angstrom. As expected, the triiodide anion in 4 is situated differently. In contrast to compound 2, the I3- anion in 4 is perpendicular to the fulvalenide ligand. The features in the variable-temperature (77-300 K) Fe-57 Mossbauer spectra of 1 include two doublets, which are expected for a mixed-valence cation localized on the time scale of the Mossbauer technique (electron-transfer rates less than approximately 10(7) s-1). The valence-trapped electronic structure is also seen for compound 3. In the case of 2, at temperatures below 150 K it shows two doublets in the Fe-57 Mossbauer spectra and increasing the temperature causes two doublets to become a single ''average-valence'' doublet at a temperature of approximately 200 K. In comparison with compounds 1-3, a single ''average-valencec doublet (DELTA-E(Q) almost-equal-to 1.1 mm s-1) is seen even at 77 K for 4 and 5. Thus, there is a dramatic change in electron-transfer rate as the position of halide substituent in the benzyl unit is changed from the para position to the ortho position. EPR and IR data are also presented for 1-5.

  DOI：

  10.1021/om00038a012
• 作为产物：
  描述：

  1,1''-biferrocene 、 2-溴苯甲酰氯 在 AlCl₃ 、 Na₂S₂O₃ 作用下， 以 二氯甲烷 为溶剂， 以40%的产率得到1,1'''-bis(o-bromobenzoyl)biferrocene
  参考文献：
  名称：

  取代基对混合价三碘化三碘化亚铁络合物中分子内电子转移速率的显著作用

  摘要：

  The factors controlling the rate of intramolecular electron transfer in the solid state have been studied for a series of binuclear mixed-valence 1',1'''-bis(substituted benzyl)biferrocenium triiodide salts, where the substituents in the benzyl unit are p-iodo (1), p-bromo (2), p-chloro (3), o-iodo (4), and o-bromo (5). The X-ray structure of neutral 1',1'''-bis(p-bromobenzyl)biferrocene has been determined at 298 K: P1BAR, a = 5.853 (4) angstrom, b = 8.380 (3) angstrom, c = 14.2295 (18) angstrom, alpha = 74.622 (15)-degrees, beta = 83.940 (23)-degrees, and gamma = 86.69 (4)-degrees; Z = 1, D(calcd) = 1.758 g cm-8, R(F) = 0.036, and R(wF) = 0.038. The Fe-Fe distance is 5.119 (3) angstrom. Compound 2 crystallizes in the triclinic space group P1BAR with one molecule in a unit cell with dimensions a = 9.5505 (24) angstrom, b = 10.984 (3) angstrom, c = 11.248 (5) angstrom, alpha = 119.71 (3)-degrees, beta = 116.04 (3)-degrees, and gamma = 76.946 (22)-degrees. The final discrepancy factors are R(F) = 0.052 and R(wF) = 0.039. A decrease in Fe-Fe distance (5.058 (7) angstrom) has been observed when 1',1'''-bis(p-bromobenzyl)biferrocene is oxidized. The solid-state structure of 2 is composed of parallel sheets of cations and polyiodide ions which contain zigzag chains of alternate I3- and I2 units. The distance of 3.487 (2) angstrom between neighboring iodine atoms in I2 and I3- units within a chain indicates a nonnegligible interaction. Compound 4 crystallizes in the triclinic space group P1BAR with one molecule in a unit cell with dimensions a = 8.149 (4) angstrom, b = 9.567 (3) angstrom, c = 12.491 (4) angstrom, alpha = 111.78 (3)-degrees, beta = 85.97 (4)-degrees, and gamma = 108.39 (3)-degrees. The final discrepancy factors for 4 and R(F) = 0.056 and R(wF) = 0.04. The Fe-Fe distance in 4 is 5.082 (8) angstrom. As expected, the triiodide anion in 4 is situated differently. In contrast to compound 2, the I3- anion in 4 is perpendicular to the fulvalenide ligand. The features in the variable-temperature (77-300 K) Fe-57 Mossbauer spectra of 1 include two doublets, which are expected for a mixed-valence cation localized on the time scale of the Mossbauer technique (electron-transfer rates less than approximately 10(7) s-1). The valence-trapped electronic structure is also seen for compound 3. In the case of 2, at temperatures below 150 K it shows two doublets in the Fe-57 Mossbauer spectra and increasing the temperature causes two doublets to become a single ''average-valence'' doublet at a temperature of approximately 200 K. In comparison with compounds 1-3, a single ''average-valencec doublet (DELTA-E(Q) almost-equal-to 1.1 mm s-1) is seen even at 77 K for 4 and 5. Thus, there is a dramatic change in electron-transfer rate as the position of halide substituent in the benzyl unit is changed from the para position to the ortho position. EPR and IR data are also presented for 1-5.

  DOI：

  10.1021/om00038a012