{(1,1'-biphenyl-2-yl)(dimethylamino)methylene}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)(dimethylamino)methylene}pentacarbonylchromium
• 英文别名: pentacarbonyl[(N,N-dimethylamino)(2-biphenyl)carbene]chromium(0)；Carbon monoxide;[dimethylamino-(2-phenylphenyl)methylidene]chromium
• 化学式: C₂₀H₁₅CrNO₅
• 分子量: 401.339
• InChiKey: ULZICAJBMWZTLM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.75
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  8.2
• 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)(dimethylamino)methylene}pentacarbonylchromium 以 1,4-二氧六环 为溶剂， 以29%的产率得到{{(1',2',3',4',5',6'-η)-1,1'-biphenyl-2-yl}(dimethylamino)methylene}dicarbonylchromium
  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：

  N,N-dimethylbiphenyl-2-carboxamide 、 六羰基铬 在 sodium naphthalenide 、 trimethylchlorosilane 作用下， 以 四氢呋喃 为溶剂， 以63%的产率得到{(1,1'-biphenyl-2-yl)(dimethylamino)methylene}pentacarbonylchromium
  参考文献：
  名称：

  铬的对映体纯的轴向手性氨基碳烯配合物

  摘要：

  在具有甲基Aminocarbene络合物的邻位上的芳环上的aminocarbene部分，（小号）-pentacarbonyl [（N，N-二甲基氨基）（3-甲氧羰基-2-甲基苯基）卡宾]铬（0）[ （S）-6 ]和（R）-五羰基[（N，N-二甲基氨基）（5-甲氧基羰基-2-甲基苯基）卡宾]铬（0）[ （R）-7 ]是通过对映体纯的形式制备的（S）-1-（1-萘基）乙醇结晶非对映异构体酯。在的情况下（小号）-6消旋屏障Δ ģ ⧧建立了rac＝ 121±0.5kJ·mol -1。的取代ø -甲基组与异丙基几乎没有改变外消旋屏障（Δ ģ ⧧rac = 120.5±0.5 kJ·mol -1），而邻苯基的引入导致ΔG substantial大大降低赛车。尝试在配合物（S -6）和（R -7）与炔烃的热反应中转移手性，钯催化插入C-H键，以及光化学形成β-内酰胺均未成功。

  DOI：

  10.1021/om701188p

文献信息

• 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.
• Enantiomerically Pure Axially Chiral Aminocarbene Complexes of Chromium
  作者：Luděk Meca、Ivana Císařová、Dušan Drahoňovský、Dalimil Dvořák

  DOI：10.1021/om701188p

  日期：2008.4.1

  N-dimethylamino)(3-methoxycarbonyl-2-methylphenyl)carbene]chromium(0) [(S)-6] and (R)-pentacarbonyl[(N,N-dimethylamino)(5-methoxycarbonyl-2-methylphenyl)carbene]chromium(0) [(R)-7], were prepared in enantiomerically pure form by the crystallization of diastereoisomeric esters with (S)-1-(1-naphthyl)ethanol. In the case of (S)-6 the racemization barrier ΔG⧧rac = 121 ± 0.5 kJ·mol−1 was established. The substitution

  在具有甲基Aminocarbene络合物的邻位上的芳环上的aminocarbene部分，（小号）-pentacarbonyl [（N，N-二甲基氨基）（3-甲氧羰基-2-甲基苯基）卡宾]铬（0）[ （S）-6 ]和（R）-五羰基[（N，N-二甲基氨基）（5-甲氧基羰基-2-甲基苯基）卡宾]铬（0）[ （R）-7 ]是通过对映体纯的形式制备的（S）-1-（1-萘基）乙醇结晶非对映异构体酯。在的情况下（小号）-6消旋屏障Δ ģ ⧧建立了rac＝ 121±0.5kJ·mol -1。的取代ø -甲基组与异丙基几乎没有改变外消旋屏障（Δ ģ ⧧rac = 120.5±0.5 kJ·mol -1），而邻苯基的引入导致ΔG substantial大大降低赛车。尝试在配合物（S -6）和（R -7）与炔烃的热反应中转移手性，钯催化插入C-H键，以及光化学形成β-内酰胺均未成功。