{(1,1'-biphenyl-2-yl)methoxymethylene}pentacarbonylchromium

• 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: {(1,1'-biphenyl-2-yl)methoxymethylene}pentacarbonylchromium
• 英文别名: Carbon monoxide;[methoxy-(2-phenylphenyl)methylidene]chromium
• 化学式: C₁₉H₁₂CrO₆
• 分子量: 388.297
• InChiKey: ZKVVNAXAJMRLKX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.84
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  14.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  {(1,1'-biphenyl-2-yl)methoxymethylene}pentacarbonylchromium 在 CO 作用下， 以 四氢呋喃 为溶剂， 以62%的产率得到六羰基铬
  参考文献：
  名称：

  环状（芳烃）铬卡宾配合物的合成，结构和反应活性

  摘要：

  In contrast to benzannulation products obtained by photolysis, thermolysis of the chromium carbene complexes [(1,1'-biphenyl-2-yl)methoxymethylene]pentacarbonylchromium (1) and [(1,1'-biphenyl-2-yl)(dimethylamino)methylene]pentacarbonylchromium (4) provide the new cyclic arene carbene complexes {[(1',2',3',4',5',6'-eta)-1,1'-biphenyl-2-yl]methoxymethylene}dicarbonylchromium (3) and {[(1',2',3',4',5',6'-eta)-1,1'-biphenyl-2-yl](dimethylamino)methylene}dicarbonylchromium (5). The C-13 NMR spectra of these new complexes have unusually high-field-shifted and low-field-shifted signals for the carbene and carbonyl carbon resonances, respectively. The complexes are remarkably stable and do not show the high electrophilic behavior typical of Fischer carbene complexes. A new protocol for the aminolysis of Fischer carbene complexes is reported. The structure of complexes 3 and 5 were determined by single-crystal X-ray diffraction studies. 3 crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 16.154 (2) angstrom, b = 12.256 (2) angstrom, c = 15.575 (2) angstrom, and beta = 122.92 (1)-degrees, with Z = 8. 5 crystallizes in the monoclinic space group P2(1)/n with unit cell dimensions a = 11.47 (1) angstrom, b = 7.082 (7) angstrom, c = 20.87 (2) angstrom, and beta = 108.13 (2)-degrees, with Z = 4. The structures were refined by full-matrix least-squares procedures to final R = 0.028 and R(w) = 0.050 for 2074 unique observed reflections for 3 and R = 0.066 and R(w) = 0.101 for 1580 unique observed reflections for 5.

  DOI：

  10.1021/om00037a066
• 作为产物：
  描述：

  2-碘联苯 、 六羰基铬 、 三氟甲烷磺酸甲酯 在 t-C₄H₉Li 、 NaHCO₃ 作用下， 以 乙醚 、 正戊烷 为溶剂， 以96%的产率得到{(1,1'-biphenyl-2-yl)methoxymethylene}pentacarbonylchromium
  参考文献：
  名称：

  环状（芳烃）铬卡宾配合物的合成，结构和反应活性

  摘要：

  In contrast to benzannulation products obtained by photolysis, thermolysis of the chromium carbene complexes [(1,1'-biphenyl-2-yl)methoxymethylene]pentacarbonylchromium (1) and [(1,1'-biphenyl-2-yl)(dimethylamino)methylene]pentacarbonylchromium (4) provide the new cyclic arene carbene complexes {[(1',2',3',4',5',6'-eta)-1,1'-biphenyl-2-yl]methoxymethylene}dicarbonylchromium (3) and {[(1',2',3',4',5',6'-eta)-1,1'-biphenyl-2-yl](dimethylamino)methylene}dicarbonylchromium (5). The C-13 NMR spectra of these new complexes have unusually high-field-shifted and low-field-shifted signals for the carbene and carbonyl carbon resonances, respectively. The complexes are remarkably stable and do not show the high electrophilic behavior typical of Fischer carbene complexes. A new protocol for the aminolysis of Fischer carbene complexes is reported. The structure of complexes 3 and 5 were determined by single-crystal X-ray diffraction studies. 3 crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 16.154 (2) angstrom, b = 12.256 (2) angstrom, c = 15.575 (2) angstrom, and beta = 122.92 (1)-degrees, with Z = 8. 5 crystallizes in the monoclinic space group P2(1)/n with unit cell dimensions a = 11.47 (1) angstrom, b = 7.082 (7) angstrom, c = 20.87 (2) angstrom, and beta = 108.13 (2)-degrees, with Z = 4. The structures were refined by full-matrix least-squares procedures to final R = 0.028 and R(w) = 0.050 for 2074 unique observed reflections for 3 and R = 0.066 and R(w) = 0.101 for 1580 unique observed reflections for 5.

  DOI：

  10.1021/om00037a066

文献信息

• Optically Active (<i>aR</i>)- and (<i>aS</i>)-Linear and Vaulted Biaryl Ligands: Deracemization versus Oxidative Dimerization
  作者：Gang Hu、Daniel Holmes、Brina Fay Gendhar、William D. Wulff

  DOI：10.1021/ja903820m

  日期：2009.10.14

  The copper-mediated deracemization of the C2-symmetric vaulted biaryl ligands VANOL and VAPOL has been investigated. In the course of the studies that have led to a more reliable procedure for this process, an unprecedented oxidative dimerization of these ligands has been uncovered. The structures of these oxidative dimerization products were elucidated by a series of NMR experiments, and these assignments were supported by other spectroscopic techniques as well as their chemical reactivity. This oxidative dimerization process was not observed for the linear biaryl ligands BANOL and BINOL, although the new deracemization procedure was effective for the generation of BINOL with high optical purity. The (aS)-enantiomers of BINOL, VANOL and VAPOL were accessible with a copper complex of (-)-sparteine, and the (aR)-enantiomeric series were accessible with a copper complex of O'Brien's diamine. Both sparteine and O'Brien's diamine give higher optical purities with VANOL and VAPOL than with BINOL, and this is consistent with the steric congestion present in the matched and mismatched copper complexes of these diamines with the biaryl ligands.
• Cyclization reactions of chromium dienylcarbene complexes. Entry to ortho-substituted aromatic alcohols via a designed photoreaction
  作者：Craig A. Merlic、Daqiang Xu

  DOI：10.1021/ja00019a047

  日期：1991.9
• Synthesis, structure, and reactivity of cyclic (arene)chromium carbene complexes
  作者：Craig A. Merlic、Daqiang Xu、Saeed I. Khan

  DOI：10.1021/om00037a066

  日期：1992.1

  In contrast to benzannulation products obtained by photolysis, thermolysis of the chromium carbene complexes [(1,1'-biphenyl-2-yl)methoxymethylene]pentacarbonylchromium (1) and [(1,1'-biphenyl-2-yl)(dimethylamino)methylene]pentacarbonylchromium (4) provide the new cyclic arene carbene complexes [(1',2',3',4',5',6'-eta)-1,1'-biphenyl-2-yl]methoxymethylene}dicarbonylchromium (3) and [(1',2',3',4',5',6'-eta)-1,1'-biphenyl-2-yl](dimethylamino)methylene}dicarbonylchromium (5). The C-13 NMR spectra of these new complexes have unusually high-field-shifted and low-field-shifted signals for the carbene and carbonyl carbon resonances, respectively. The complexes are remarkably stable and do not show the high electrophilic behavior typical of Fischer carbene complexes. A new protocol for the aminolysis of Fischer carbene complexes is reported. The structure of complexes 3 and 5 were determined by single-crystal X-ray diffraction studies. 3 crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 16.154 (2) angstrom, b = 12.256 (2) angstrom, c = 15.575 (2) angstrom, and beta = 122.92 (1)-degrees, with Z = 8. 5 crystallizes in the monoclinic space group P2(1)/n with unit cell dimensions a = 11.47 (1) angstrom, b = 7.082 (7) angstrom, c = 20.87 (2) angstrom, and beta = 108.13 (2)-degrees, with Z = 4. The structures were refined by full-matrix least-squares procedures to final R = 0.028 and R(w) = 0.050 for 2074 unique observed reflections for 3 and R = 0.066 and R(w) = 0.101 for 1580 unique observed reflections for 5.