| 101792-52-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 101792-52-3
• 化学式: C₁₈H₁₈Mg
• 分子量: 258.646
• InChiKey: PNILBQOGVHVTPM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.95
• 重原子数：
  19.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  (η-pentamethylcyclopentadienyl)(nitrosyl)dichlorotungsten 、 以 四氢呋喃 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η³-allyl) Complexes

  摘要：

  Sequential treatment at low temperatures of Cp*W(NO)Cl-2 in THF with 1 equiv of a binary magnesium allyl reagent, followed by an excess of LiBH4, affords three new Cp*W(NO)(H)(eta(3)-allyl) complexes, namely, 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). Complexes 1-3 are isolable as air-stable, analytically pure yellow solids in good to moderate yields by chromatography or fractional crystallization. In solutions, complex 1 exists as two coordination isomers in an 83:17 ratio differing with respect to the endo/ exo orientation of the allyl ligand. In contrast, complexes 2 and 3 each exist as four coordination isomers, all differing by the orientation of their allyl ligands which can have either an endo or an exo orientation with the phenyl or methyl groups being either proximal or distal to the nitrosyl ligand. A DFT computational analysis using the major isomer of Cp*W(NO)(H)(eta(3)-CH2CHCHMe) (3a) as the model complex has revealed that its lowest-energy thermal-decomposition pathway involves the intramolecular isomerization of 3a to the 16e eta(2)-alkene complex, Cp*W(NO)(eta(2)center dot CH2=CHCH2Me). Such eta(2)-alkene complexes are isolable as their 18e PMe3 adducts when compounds 1-3 are thermolyzed in neat PMe3, the other organometallic products formed during. these thermolyses being Cp*W(NO)(PMe3)(2) (5) and, occasionally, Cp*W(NO)(H)(eta(1)-allyl)(PMe3). 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.

  DOI：

  10.1021/acs.inorgchem.5b00747

文献信息

• [EN] PROCESS FOR DEHYDROGENATION OF ALKYL-CONTAINING COMPOUNDS USING MOLYBDENUM AND TUNGSTEN NITROSYL COMPLEXES<br/>[FR] PROCÉDÉ POUR LA DÉSHYDROGÉNATION DE COMPOSÉS CONTENANT UN GROUPEMENT ALKYLE À L'AIDE DE COMPLEXES NITROSYLÉS DE MOLYBDÈNE ET DE TUNGSTÈNE
  申请人：DOW GLOBAL TECHNOLOGIES LLC

  公开号：WO2016112237A1

  公开（公告）日：2016-07-14

  A process for the dehydrogenation of alkyl-containing compounds comprises reacting an alkyl-containing compound and a Group VI nitrosyl complex characterized as a transition metal complex having the composition Cp'M(NO)(R1)(R2), wherein Cp' is selected from certain substituted and unsubstituted η5-cyclopentadienyl groups; M is W or Mo; and R1 and R2 are independently selected from CH2C(CH3)3; CH2Si(CH3)3; CH2(C6H5); CH3; hydrogen; and η3-allyl; provided that if R1 is hydrogen, R2 is η3-allyl; under conditions such that the alkyl-containing compound is converted to an olefin, and in particular embodiments, a terminal olefin. The dehydrogenation can be carried out using a neat and/or undried alkyl-containing compound and/or may be conducted under air, and does not require a sacrificial olefin to drive the reaction, thereby increasing convenience and decreasing cost in comparison with some other dehydrogenation processes.

  一种去氢化含烷基化合物的方法包括将一种烷基化合物与一种被表征为具有组成Cp'M(NO)(R1)(R2)的过渡金属配合物的第六族亚硝基复合物反应，其中Cp'从某些取代和未取代的η5-环戊二烯基团中选择；M为W或Mo；R1和R2分别从 C(CH3)3；CH2Si( )3；CH2(C6H5)； ；氢；和η3-烯丙基中选择；条件是如果R1为氢，则R2为η3-烯丙基；在这些条件下，烷基化合物被转化为烯烃，特别是末端烯烃。该去氢化可以使用纯净和/或未干燥的烷基化合物进行，和/或可以在空气中进行，并且不需要牺牲性烯烃来推动反应，从而增加了便利性并降低了成本，与其他一些去氢化过程相比。