{η2-phenyl(trimethylsilyl)ethyne}(trimethylphosphane)zirconocene

• 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: {η2-phenyl(trimethylsilyl)ethyne}(trimethylphosphane)zirconocene
• 英文别名: [(η5-C5H5)2Zr(η2-Me3SiCCPh)(PMe3)]
• 化学式: C₂₄H₃₃PSiZr
• 分子量: 471.809
• InChiKey: LAKMZFLKWYMPNO-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：
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• 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：

  {η2-phenyl(trimethylsilyl)ethyne}(trimethylphosphane)zirconocene 、 3,3-二甲基环丙烯 在 三乙基硼 作用下， 以 正戊烷 为溶剂， 以37%的产率得到2,2-bis(η5-cyclopentadienyl)-6,6-dimethyl-4-phenyl-3-trimethylsilyl-2-zirconabicyclo{3.1.0}hex-3-ene
  参考文献：
  名称：

  Binger, Paul; Mueller, Patrik; Langhauser, Franz, Chemische Berichte, 1993, vol. 126, # 7, p. 1541 - 1550

  摘要：

  DOI：
• 作为产物：
  描述：

  zirconocene(1-butene)(PMe3) 、 苯基乙炔基三甲基硅烷 以 乙醚 、 正戊烷 为溶剂， 以63%的产率得到{η2-phenyl(trimethylsilyl)ethyne}(trimethylphosphane)zirconocene
  参考文献：
  名称：

  Binger, Paul; Mueller, Patrik; Langhauser, Franz, Chemische Berichte, 1993, vol. 126, # 7, p. 1541 - 1550

  摘要：

  DOI：

文献信息

• Reactionsof in situ generated (η2-phenyltrimethylsilylacetylene)zirconocene
  作者：Gerhard Erker、Roland Zwettler

  DOI：10.1016/0022-328x(91)86143-e

  日期：1991.5

  reactive intermediate 3 is protonated to give Cp2Zr(CR1=CHR2)(μ-OC)W(CO)2CP (12, R1 = SiMe3, R2 = Ph). Treatment of 1 with [HNEt3][BPh4] in acetonitrile gives the cationic Cp2Zr(CR1=CR2CMe=NH)(CH3CN)+ (3a: R1 = SiMe3, R2 = Ph) and its regioisomer 13b (R1 and R2 exchanged). There is evidence that the complexes 13 are formed by acetonitrile addition to thermally-generated 3 to give Cp2Zr(CR1=CR2CMe=N), which

  五元金属环的CP 2 Zr的（CR1 = CR2CR2 = CR 1）（1，R 1 =森达3，R 2 = PH）是用于一个合适的起始材料在原位生成活性（η的2 -phenyltrimethylsilylethyne）二茂锆（3）。因此，用三甲基膦将1（70°C）热解，得到CP 2 Zr（Me 3 SiC * z.tbnd; CPh）（PMe 3）（8）和游离的Me 3 SiC CPh（4）。随后8与苯乙酮反应生成CP 2Zr [CR1 ＝ CR2CMePhO]（9，R 1＝ SiMe 3，R 2＝ Ph）。在CPW（CO）3 H存在下对1的热解也导致释放出1当量的4。反应性中间体3被质子化以得到CP 2 Zr（CR 1＝ CHR 2）（μ-OC）W（CO）2 CP（12，R 1＝ SiMe 3，R 2＝ Ph）。用乙腈中的[HNEt 3 ] [BPh 4 ]处理1，得到阳离子CP 2Zr（CR1
• Mechanism of Reversible Alkyne Coupling at Zirconocene:  Ancillary Ligand Effects
  作者：Adam D. Miller、Jennifer L. McBee、T. Don Tilley

  DOI：10.1021/ja800025u

  日期：2008.4.1

  The mechanism of reversible alkyne coupling at zirconium was investigated by examination of the kinetics of zinconacyclopentadiene cleavage to produce free alkynes. The zirconacyclopentadiene rings studied possess trimethylsilyl substituents in the a-positions, and the ancillary Cp-2, Me2C(eta(5)-C5H4)(2), and CpCp* (Cp* = eta(5)-C5Me5) bis(cyclopentadienyl) ligand sets were employed. Fragmentation of the zirconacyclopentadiene ring in Cp2Zr[2,5-(Me3Si)(2)-3,4-Ph2C4] with PMe3, to produce Cp2Zr(eta(5)-PhC CSiMe3)- (PMe3) and free PhC CSiMe3, is first-order in initial zirconacycle concentration and zero-order in incoming phosphine (k(obs) = 1.4(2) x 10(-5) s(-1) at 22 degrees C), and the activation parameters determined by an Eyring analysis (Delta H-double dagger = 28(2) kcal mol(-1) and Delta S-double dagger = 14(4) eu) are consistent with a dissociative mechanism. The analogous reaction of the ansa-bridged complex Me2C(eta(5)-C5H4)(2)Zr[2,5-(Me3Si)(2)-3,4-Ph2C4] is 100 times faster than that for the corresponding Cp-2 complex, while the corresponding CpCp* complex reacts 20 times slower than the Cp-2 derivative. These rates appear to be largely influenced by the steric properties of the ancillary ligands.