bis(tetramethylphospholyl)chromium | 195724-76-6

• 英文名称: bis(tetramethylphospholyl)chromium
• 英文别名: octamethyl-1,1'-diphosphachromocene
• CAS: 195724-76-6
• 化学式: C₁₆H₂₄CrP₂
• 分子量: 330.31
• InChiKey: LJBBNPGIFLDZTQ-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：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(η(5)-C5H4Me)2Fe][B(C6H5)4] 、 bis(tetramethylphospholyl)chromium 以 四氢呋喃 为溶剂， 以65%的产率得到bis(tetramethylphospholyl)chromium tetraphenylborate
  参考文献：
  名称：

  Octamethyl-1,1‘-diphosphachromocene:  Its Spin Distribution and Oxidation

  摘要：

  Octamethyl-1,1'-diphosphachromocene ((Tmp)(2)Cr) was prepared from (Tmp)K and chromium dichloride in 81% yield, According to X-ray analysis, it has a distorted sandwich structure with the P atoms being bent away from chromium. Large H-1, C-13, and P-31 NMR shifts established the similarity to chromocenes (S = 1) and negative spin on the ligands. The signal splitting and temperature-dependent H-1 NMR data revealed that, on the ligand, the spin sits predominantly at the phosphorus and two carbon atoms. In the cyclic voltammetry, two oxidation steps and one reduction were visible. After chemical oxidation, [(Tmp)(2)Cr](+)[B(C6H5)(4)](-) was isolated in 65% yield. Its EPR spectrum is in accord with a S = 3/2 species. The H-1 NMR spectrum resembled those of chromocenium ions. Its analysis and that of the temperature-dependent 1H NMR spectra indicated a rather uniform spin distribution within the ligands. It was concluded that, in any case, the phosphorus may release spin to neighboring molecules.

  DOI：

  10.1021/om9705618
• 作为产物：
  描述：

  CrCl₂·THF 、 potassium 2,3,4,5-tetramethylphospholide 以 四氢呋喃 为溶剂， 以80.7%的产率得到bis(tetramethylphospholyl)chromium
  参考文献：
  名称：

  Octamethyl-1,1‘-diphosphachromocene:  Its Spin Distribution and Oxidation

  摘要：

  Octamethyl-1,1'-diphosphachromocene ((Tmp)(2)Cr) was prepared from (Tmp)K and chromium dichloride in 81% yield, According to X-ray analysis, it has a distorted sandwich structure with the P atoms being bent away from chromium. Large H-1, C-13, and P-31 NMR shifts established the similarity to chromocenes (S = 1) and negative spin on the ligands. The signal splitting and temperature-dependent H-1 NMR data revealed that, on the ligand, the spin sits predominantly at the phosphorus and two carbon atoms. In the cyclic voltammetry, two oxidation steps and one reduction were visible. After chemical oxidation, [(Tmp)(2)Cr](+)[B(C6H5)(4)](-) was isolated in 65% yield. Its EPR spectrum is in accord with a S = 3/2 species. The H-1 NMR spectrum resembled those of chromocenium ions. Its analysis and that of the temperature-dependent 1H NMR spectra indicated a rather uniform spin distribution within the ligands. It was concluded that, in any case, the phosphorus may release spin to neighboring molecules.

  DOI：

  10.1021/om9705618

文献信息

• Low-spin 1,1′-diphosphametallocenates of chromium and iron
  作者：Samuel M. Greer、Ökten Üngor、Ross J. Beattie、Jaqueline L. Kiplinger、Brian L. Scott、Benjamin W. Stein、Conrad A. P. Goodwin

  DOI：10.1039/d0cc06518h

  日期：——

  We report two anionic diphosphametallocenates, [K(2.2.2-crypt)][M(PC4Me4)2] (M = Cr, 2-Cr; Fe, 2-Fe). Both are low-spin (S = ½) by EPR spectroscopy and SQUID magnetometry. This contrasts the high-spin (S = ) ferrocenate, [K(2.2.2-crypt)][Fe(C5H2-1,2,4-tBu)2] (4-Fe). Quantum chemical calculations suggest this is due to significant differences in ligand field splitting of the d-orbitals which also explain

  我们报告了两个阴离子二磷酸金属分配，[K（2.2.2-crypt）] [M（PC 4 Me 4）2 ]（M = Cr，2-Cr ; Fe，2-Fe）。通过EPR光谱和SQUID磁力计，两者均为低转速（S =½）。这与高自旋（S = ）二茂铁酸盐[K（2.2.2-crypt）] [Fe（C 5 H 2 -1,2,4- t Bu）2 ]（4-Fe）形成对比。量子化学计算表明，这是由于d轨道配体场分裂的显着差异，这也解释了2-M络合物的结构特征。