lithium (2-P,P-dimethylphosphanylethyl)tetramethylcyclopentadienide | 866607-56-9

• 分子结构分类: 有机化合物
• 英文名称: lithium (2-P,P-dimethylphosphanylethyl)tetramethylcyclopentadienide
• CAS: 866607-56-9
• 化学式: C₁₃H₂₂P*Li
• 分子量: 216.232
• InChiKey: BILPNQVDRCRDQW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.93
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  lithium (2-P,P-dimethylphosphanylethyl)tetramethylcyclopentadienide 、 pentamethylcyclopentadienylzirconium(IV) trichloride 以 四氢呋喃 为溶剂， 以58%的产率得到(η5-(2-P,P-dimethylphosphanylethyl)tetramethylcyclopentadienyl)(η5-pentamethylcyclopentadienyl)dichlorozirconium(IV)
  参考文献：
  名称：

  Mono- and bis-[2-(P,P-dimethylphosphanyl)ethyl]tetramethylcyclopentadienyl zirconium(IV) complexes: Synthesis and structural studies in crystalline state and in solutions

  摘要：

  Synthetic routines for a new ligand C5Me4CH2CH2PMe2 (2b) in forms of its Li- (2b-Li), Na- (2b-Na) salts and in the CH-form (2b-H), as well as for silanes Me3Si-C5H4CH2CH2PMe2 (3a) and Me3Si-C5Me4CH2CH2PMe2 (3b) have been developed. On the basis of it, new half-sandwich [eta(5) :eta(1)-kappa P-C5H4CH2CH2PMe2]ZrCl3 (4a), [eta(5):eta(1)-kappa P-C5Me4CH2CH2PMe2]ZrCl3 (4b) and sandwich [eta(5)-C5Me4CH2CH2PMe2](2)ZrCl2 (5), [eta(5)-C5Me4CH2CH2PMe2][eta(5)-C5Me5]ZrCl3 (6) complexes of Zr(IV) have been prepared and characterized. Along with them, the first example of X-ray structurally characterized dinuclear Zr(IV) complex incorporating both sandwich (6) and half-sandwich (4b) moieties linked one to another by means of Zr P coordination bond 7, has been described. Formation of an analogously organized trinuclear complex 8, built from one sandwich fragment of 5 and two half-sandwich fragments of 4b was proved by NMR spectroscopy methods. Molecular structures of half-sandwich complexes in their solvent-free dimeric forms (4a and 4b) and as 1: 1 adducts with THF (4a-THF and 4b-THF) along with those of dinuclear complex 7 have been established by X-ray diffraction analyses. The dynamic behavior for di- and trinuclear complexes 7 and 8, due to the intermolecular dissociation-coordination of the Me2P-groups in THF-d(8) solutions has been studied by variable-temperature NMR spectroscopy. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.06.008
• 作为产物：
  描述：

  二甲基磷化锂 、 4,5,6,7-tetramethylspiro<2,4>-hepta-4,6-diene 以 四氢呋喃 为溶剂， 以59%的产率得到lithium (2-P,P-dimethylphosphanylethyl)tetramethylcyclopentadienide
  参考文献：
  名称：

  Mono- and bis-[2-(P,P-dimethylphosphanyl)ethyl]tetramethylcyclopentadienyl zirconium(IV) complexes: Synthesis and structural studies in crystalline state and in solutions

  摘要：

  Synthetic routines for a new ligand C5Me4CH2CH2PMe2 (2b) in forms of its Li- (2b-Li), Na- (2b-Na) salts and in the CH-form (2b-H), as well as for silanes Me3Si-C5H4CH2CH2PMe2 (3a) and Me3Si-C5Me4CH2CH2PMe2 (3b) have been developed. On the basis of it, new half-sandwich [eta(5) :eta(1)-kappa P-C5H4CH2CH2PMe2]ZrCl3 (4a), [eta(5):eta(1)-kappa P-C5Me4CH2CH2PMe2]ZrCl3 (4b) and sandwich [eta(5)-C5Me4CH2CH2PMe2](2)ZrCl2 (5), [eta(5)-C5Me4CH2CH2PMe2][eta(5)-C5Me5]ZrCl3 (6) complexes of Zr(IV) have been prepared and characterized. Along with them, the first example of X-ray structurally characterized dinuclear Zr(IV) complex incorporating both sandwich (6) and half-sandwich (4b) moieties linked one to another by means of Zr P coordination bond 7, has been described. Formation of an analogously organized trinuclear complex 8, built from one sandwich fragment of 5 and two half-sandwich fragments of 4b was proved by NMR spectroscopy methods. Molecular structures of half-sandwich complexes in their solvent-free dimeric forms (4a and 4b) and as 1: 1 adducts with THF (4a-THF and 4b-THF) along with those of dinuclear complex 7 have been established by X-ray diffraction analyses. The dynamic behavior for di- and trinuclear complexes 7 and 8, due to the intermolecular dissociation-coordination of the Me2P-groups in THF-d(8) solutions has been studied by variable-temperature NMR spectroscopy. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.06.008

文献信息

• Reduction of bis[(2-phosphinoethyl)tetramethyl-cyclopentadienyl]zirconium dichlorides: intramolecular C-H activation vs. stabilization of the low-valence metal center
  作者：D. P. Krut’ko、M. V. Borzov、E. N. Veksler、R. S. Kirsanov

  DOI：10.1007/s11172-008-0010-2

  日期：2008.1

  afforded the fulvene hydride complexes Zr(H)(η5−C5Me5)[η5:η2(C,P)−(CH2)C5Me3CH2CH2PR2] (R = Me (7), Ph (8)); in the case of compound 2, the aryl hydride Zr(H)(η5:C5Me5)[η5:η1(C)−C5Me4CH2CH2PPh(o−C6H4)] (9) was also formed. The reduction of complexes 3 and 4 gave the ZrII derivatives Zr[η5:η1(P)− C5Me4CH2CH2PMe2]2 (12) and Zr[η5:η1(P)−C5Me4CH2CH2PMe2][η5:η1(P)−C5Me4CH2 CH2PPh2] (14) stabilized by two phosphine

  R2P 官能化二氯化锆 [C5Me4(CH2)2PR2] (C5Me5)ZrCl2（R = Me (1) 和 Ph (2)）和 [C5Me4( )2PMe2][C5Me4( )2PR2]ZrCl2 (R) 的还原= Me (3) 和 Ph (4)) 与混合镁进行了研究。在化合物 1 和 2 的还原过程中，分子内 CH 活化高度选择性地提供了富烯氢化物配合物 Zr(H)(η5−C5Me5)[η5:η2(C,P)−( )C5Me3 PR2] (R = Me (7) , 博士 (8)); 在化合物2的情况下，还形成芳基氢化物Zr(H)(η5:C5Me5)[η5:η1(C)-C5Me4 PPh(o-C6H4)](9)。配合物 3 和 4 的还原得到 ZrII 衍生物 Zr[η5:η1(P)− C5Me4 PMe2]2 (12) 和 Zr[η5:η1(P)−