4,5,6,7-tetramethylspiro<2,4>-hepta-4,6-diene | 198331-54-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 4,5,6,7-tetramethylspiro<2,4>-hepta-4,6-diene
• 英文别名: 4,5,6,7-tetramethyl-spiro-[2,4]-hepta-2,4-diene；1,2,3,4-tetramethylbicyclo[2,4]hepta-1,3-diene；4,5,6,7-tetramethylspiro[2,4]hepta-4,6-diene；4,5,6,7-Tetramethylspiro[2.4]hepta-4,6-diene
• CAS: 198331-54-3
• 化学式: C₁₁H₁₆
• 分子量: 148.248
• InChiKey: SFDCZPLGNBKVCY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  二乙基磷化锂 、 4,5,6,7-tetramethylspiro<2,4>-hepta-4,6-diene 以 四氢呋喃 为溶剂， 反应 72.0h， 以87%的产率得到1,2,3,4-tetramethyl-5-(2-P,P-diethylphosphinoethyl)cyclopentadienyl lithium
  参考文献：
  名称：

  Stabilising Rh–P coordination by phosphanylalkylcyclopentadienyl ligands

  摘要：

  (由石化的 1,2,3,4- 四甲基-5(2-P,P-二烷基/芳基膦乙基)环戊二烯和 [RhCl(CO)2]2 合成了（膦酰基/芳基）环戊二烯配合物；比较了这些配体的电子捐赠特性，结果表明在甲醇羰基化反应条件下，PâRh 的相互作用是稳定的。

  DOI：

  10.1039/b211287f
• 作为产物：
  描述：

  lithium;trimethyl-[2-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)ethyl]azanium;iodide 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 生成 4,5,6,7-tetramethylspiro<2,4>-hepta-4,6-diene
  参考文献：
  名称：

  5-[2-(二苯基膦酰基)乙基]-1,2,3,4-四甲基环戊二烯基配体的新途径——[η5:η1-C5(CH3)4CH2CH2PPh2]ZrCl3·THF的合成与晶体结构

  摘要：

  从已知化合物[2-(二甲氨基)乙基]开始，五步合成第一个过渡金属配合物与C5(CH3)4CH2CH2PPh2配体[η5:η1-C5(CH3)4CH2CH2PPh2]ZrCl3·THF(11)据报道，四甲基环戊二烯 (4) 通过 4,5,6,7-四甲基螺[2,4]庚-4,6-二烯 (7)。环戊二烯锂 LiC5(CH3)4CH2CH2PPh2 (9)、甲硅烷基化环戊二烯 (CH3)3SiC5(CH3)4CH2CH2PPh2 (10) 和环戊二烯 HC5(CH3)4CH2CH2PPh2 (12) 被分离并表征为纯物质。锆络合物11的晶体结构通过X射线衍射分析确定。

  DOI：

  10.1002/(sici)1099-0682(199911)1999:11<1973::aid-ejic1973>3.0.co;2-u

文献信息

• Lithium 5-(2-diphenylphosphinoethyl)-1,2,3,4-tetramethylcyclopentadienide: Regioselectivity of alkylation of the tetramethylcyclopentadienide anion
  作者：D. P. Krut'ko、M. V. Borzov、E. N. Veksler、E. M. Myshakin、D. A. Lemenovskii

  DOI：10.1007/bf02498168

  日期：1998.5

  Treatment of a mixture of isomeric (2-chloroethyl)-1,2,3,4-tetramethylcyclopentadienes with lithium diphenylphosphide leads to novel 4,5,6,7-tetramethylspiro[2,4]hepta-4,6-diene among the reaction products. The reaction of spiroheptadiene obtained with excess LiPPh2 at elevated temperature affords lithium 5-(2-diphenylphosphinoethyl)-1,2,3,4-tetramethylcyclopentadienide in almost quantitative yield

  用二苯基磷化锂处理异构 (2-氯乙基)-1,2,3,4-四甲基环戊二烯的混合物，可得到新型 4,5,6,7-四甲基螺[2,4]庚-4,6-二烯。反应产物。在升高的温度下获得的螺庚二烯与过量的 LiPPh2 反应以几乎定量的产率提供 5-(2-二苯基膦基乙基)-1,2,3,4-四甲基环戊二烯锂。四甲基环戊二烯阴离子烷基化的区域选择性通过从头开始对 C5Mc4H- 进行的量子化学计算进行估计。环碳原子上的全部电荷是在巴德分子中原子碎片理论的框架内确定的。
• Stabilising Rh–P coordination by phosphanylalkylcyclopentadienyl ligands
  作者：Ann E. C. McConnell、Douglas F. Foster、Peter Pogorzelec、Alexandra M. Z. Slawin、David J. Law、David J. Cole-Hamilton

  DOI：10.1039/b211287f

  日期：2003.2.11

  (Phosphanylalkyl/aryl)cyclopentadienyl complexes have been synthesised from lithiated 1,2,3,4-tetramethyl-5(2-P,P-dialkyl/arylphosphinoethyl)cyclopentadiene and [RhCl(CO)2]2; the electron donating properties of these ligands have been compared and the P–Rh interaction is shown to be stable under methanol carbonylation reaction conditions.

  (由石化的 1,2,3,4- 四甲基-5(2-P,P-二烷基/芳基膦乙基)环戊二烯和 [RhCl(CO)2]2 合成了（膦酰基/芳基）环戊二烯配合物；比较了这些配体的电子捐赠特性，结果表明在甲醇羰基化反应条件下，PâRh 的相互作用是稳定的。
• New bridging tridentate bis-cyclopentadienyl ligands [C5Me4(CH2)n]2PPh (n = 1, 2) for organometallic synthesis
  作者：D. P. Krut’ko、R. S. Kirsanov、M. V. Borzov

  DOI：10.1007/s11172-007-0285-8

  日期：2007.9

  Preparative procedures were developed for the synthesis of new transmethylated bis-cyclopentadienyl ligands with phosphine-containing bridging fragments. These ligands were isolated as the dilithium salts Li2[(C5Me4CH2)2PPh] (1) and Li2[(C5Me4CH2CH2)2PPh] (3). Phosphorus-substituted 3-ansa-zirconocene dichloride [(C5Me4CH2)2PPh]ZrCl2 was synthesized starting from 1. The NMR spectroscopic data provide evidence for the absence of the Zr←P coordination interaction in solution. A straightforward approach to 5-ansa-zirconocene dichloride [(C5Me4CH2CH2)2PPh]ZrCl2 starting from lithium salt 3 and ZrCl4 was shown to be impossible.

  为合成带有含磷桥接片段的新型反甲基化双环戊二烯配体开发了制备程序。这些配体以二锂盐 Li2[(C5Me4CH2)2PPh] (1) 和 Li2[(C5Me4CH2CH2)2PPh] (3) 的形式分离出来。从 1 开始合成了磷取代的 3-ansa-zirconocene dichloride [(C5Me4CH2)2PPh]ZrCl2，核磁共振光谱数据证明溶液中不存在 Zr←P 配位相互作用。从锂盐 3 和 ZrCl4 开始直接合成 5-ansa-zirconocene dichloride [(C5Me4CH2CH2)2PPh]ZrCl2 是不可能的。
• Mono- and bis-[2-(P,P-dimethylphosphanyl)ethyl]tetramethylcyclopentadienyl zirconium(IV) complexes: Synthesis and structural studies in crystalline state and in solutions
  作者：Dmitrii P. Krut’ko、Maxim V. Borzov、Edward N. Veksler、Andrei V. Churakov、Lyudmila G. Kuz’mina

  DOI：10.1016/j.jorganchem.2005.06.008

  日期：2005.9

  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.
• The synthesis, characterisation and reactivity of 2-phosphanylethylcyclopentadienyl complexes of cobalt, rhodium and iridium
  作者：Ann C. McConnell、Peter J. Pogorzelec、Alexandra M. Z. Slawin、Gary L. Williams、Paul I. P. Elliott、Anthony Haynes、Andrew C. Marr、David J. Cole-Hamilton

  DOI：10.1039/b512054c

  日期：——

  oxidative addition of MeI to [Rh(C(5)H(4)(CH(2))(2)PEt(2))(CO)] and [Rh(Cp'(CH(2))(2)PPh(2))(CO)] are 62 and 1770 times faster than to [Cp*Rh(CO)(2)]. Methyl migration is slower, however. High pressure NMR studies show that [Co(Cp'(CH(2))(2)PEt(2))(CO)] and [Cp*Rh(PEt(3))(CO)] are unstable towards phosphine oxidation and/or quaternisation under methanol carbonylation conditions, but that [Rh(Cp'(CH(2))(2)PEt(2))(CO)]

  2-磷酰基乙基环戊二烯基锂化合物Li [C（5）R'（4）（CH（2））（2）PR（2）]（R = Et，R'= H或Me，R = Ph，R'= Me），已从螺碳C（5）R'（4）（C（2）H（4））与LiPR（2）的反应中制备。C（5）Et（4）HSiMe（2）CH（2）PMe（2）是由Li [C（5）Et（4）]与Me（2）SiCl（2）然后是Me（ 2）PCH（2）Li。锂盐与[RhCl（CO）（2）]（2），[IrCl（CO）（3）]或[Co（2）（CO）（8）]反应，得到[M（C（5）） R'（4）（CH（2））（2）PR（2））（CO）]（M = Rh，R = Et，R'= H或Me，R = Ph，R'= Me； M = Ir或Co，R ＝ Et，R′＝ Me），其在许多情况下在结晶学上已被表征为具有磷原子和环戊二烯基环配位的单体。这些配合物的nu（CO）值通常比环戊二烯基环和