(η5-C5Me5)W(NO)H(η3-cyclohexenyl) | 459428-96-7

• 英文名称: (η5-C5Me5)W(NO)H(η3-cyclohexenyl)
• 英文别名: (η5-C5Me5)W(NO)(η3-C6H9)(H)；[(C5(CH3)5)WH(NO)(η(3)-C6H9)]；Cp*W(NO)(η3-C6H9)(H)；Cp*W(NO)H(C6H9)
• CAS: 459428-96-7
• 化学式: C₁₆H₂₅NOW
• 分子量: 431.231
• InChiKey: AAWFCQOTIYNXLY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (η5-C5Me5)W(NO)H(η3-cyclohexenyl) 以0%的产率得到(η5-C5Me5)W(NO)(η1,η3-(cyclohexyl)cyclohexenyl
  参考文献：
  名称：

  Parallel Transformations of Cyclohexene Mediated by the Cp*W(NO) Fragment

  摘要：

  Hydrogenolysis of Cp*W(NO)(CH2CMe3)2 at room temperature in cyclohexene results in the formation of the intermediate 16e organometallic complex, [Cp*W(NO)(eta2-cyclohexene)]. This intermediate leads to three parallel transformations of cyclohexene, namely (a) C-H activation of cyclohexene to form an eta3-cyclohexenyl hydrido complex, (b) combination of cyclohexene and H2 to form a cyclohexyl hydrido complex, and (c) coupling of two molecules of cyclohexene with concomitant loss of two hydrogen atoms to form a complex containing a novel eta1,eta3-(cyclohexyl)cyclohexenyl ligand. Single-crystal X-ray crystallographic analyses of products resulting from transformations (b) and (c) have been effected.

  DOI：

  10.1021/ja0426692
• 作为产物：
  描述：

  [(C5(CH3)5)W(NO)(CH2C(CH3)3)(η(3)-CH2CCH(CH3)2)] 、 环己烷 以 环己烷 为溶剂， 以32%的产率得到(η5-C5Me5)W(NO)H(η3-cyclohexenyl)
  参考文献：
  名称：

  钨丙二烯配合物引起的异常热 C−H 键活化

  摘要：

  18e 烷基-烯丙基复合物的温和热解，CpW(NO)(CH(2)CMe(3))(eta(3)-3,3-Me(2)C(3)H(3)) (1) ，生成反应性 16e 丙二烯中间体，CpW(NO)(eta(2)-CH(2)=C=CMe(2)) (A)，伴随着通过从二甲基烯丙基配体中夺取氢而释放出新戊烷。A 已在结构上表征为其 PMe(3) 加合物，并且能够影响烃溶剂的单个和多个 CH 键活化。例如，1 与环己烷的热反应导致形成 18e 环己烯基氢化复合物，CpW(NO)(eta(3)-C(6)H(9))(H) (5)，结果烷烃溶剂的三个连续 CH 活化。

  DOI：

  10.1021/ja026951p

文献信息

• Thermal Activation of Hydrocarbon C−H Bonds Initiated by a Tungsten Allyl Complex
  作者：Stephen H. K. Ng、Craig S. Adams、Trevor W. Hayton、Peter Legzdins、Brian O. Patrick

  DOI：10.1021/ja037076q

  日期：2003.12.1

  eta(3)-H(2)CCHCMe(2)) (5) (26%) and CpW(NO)(C(6)H(3)-2,5-Me(2))(eta(3)-H(2)CCHCMe(2)) (6) (74%). Mechanistic and labeling studies indicate that the transient C-H-activating intermediates are the allene complex, CpW(NO)(eta(2)-H(2)C=C=CMe(2)) (A), and the eta(2)-diene complex, CpW(NO)(eta(2)-H(2)C=CHC(Me)=CH(2)) (B). Intermediates A and B react with cyclohexene to form CpW(NO)(eta(3)-CH(2)C(2-cyclohexenyl)CMe(2))(H)

  烯丙基复合物 CpW(NO)(CH(2)CMe(3))(eta(3)-H(2)CCHCMe(2)) (1) 在 50 摄氏度的纯碳氢化合物溶液中温和热解导致新戊烷的损失和随后激活溶剂 CH 键的瞬态中间体的产生。因此，1 与四甲基硅烷、均三甲苯和苯的热反应会影响单个 CH 活化并导致 CpW(NO)(CH(2)SiMe(3))(eta(3)-H(2)CCHCMe( 2)) (2), CpW(NO)(CH(2)C(6)H(3)-3,5-Me(2))(eta(3)-H(2)CCHCMe(2)) ( 3) 和 CpW(NO)(C(6)H(5))(eta(3)-H(2)CCHCMe(2)) (4)。1 与其他甲基取代芳烃的反应产物表明该系统对激活更强的芳烃 sp(2) CH 键具有固有的偏好。例如，对二甲苯的 CH 键活化导致形成 CpW(NO)(CH(2)C(6)H(4)-4-Me)(eta(3)-H(2)CCHCMe(2))
• Thermal Chemistry of Cp*W(NO)(H)(η³-allyl) Complexes
  作者：Rhett A. Baillie、Russell J. Wakeham、Guillaume P. Lefèvre、Aurélien Béthegnies、Brian O. Patrick、Peter Legzdins、Devon C. Rosenfeld

  DOI：10.1021/acs.organomet.5b00426

  日期：2015.7.13

  The thermal properties of Cp*W(NO)(H)(eta(3)-CH2CHCMe2) (1), Cp*W(NO)(H)(eta(3)-CH2CHCHPh) (2), and Cp*W(NO)(H)(eta(3)-CH2CHCHMe) (3) (Cp* = eta(5)-C5Me5) have been investigated. Thermolyses of 1-3 in n-pentane lead to the loss of the original,allyl ligand and the formation of the same mixture of isomeric products, namely, Cp*W(NO)(H) (eta(3)-CH2CHCHEt) (4a) and Cp*W(NO)(H)(eta(3)-MeCHCHCHMe) (4b) and their coordination isomers. Similarly, 1 reacts with cyclohexane and n-heptane to form Cp*W(NO)(H)(eta(3)-C6H9) and isomers of Cp*W(NO)(H)(eta(3)-C7H13), respectively. It is likely that complexes 1-3 first effect the selective, single-terminal C-H activation of the linear alkanes, but the first-formed products are thermally unstable and undergo two additional successive C-H activations to form the final ally]. complexes. Consistent with this view is the fact that a bis(alkyl) intermediate complex can be trapped with N-methylmorpholine. Thus, the thermolysis of 1 in N-methylmorpholine affords a single organometallic complex, Cp*W(NO)(eta(2)-CH2NC4H8O)(eta(1)-CH2CH2CHMe2) (7). Complexes 2 and 3 react with N-methylmorpholine in an identical manner. Finally, 1 effects the multiple C-H activations of 1-chloropropane and 1-chlorobutane and forms the corresponding Cp*W(NO)(Cl)(eta(3)-allyl) complexes. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.