4,4,4-trimethyl-4-methylene-4l9-hepta-2,5-diyne | 125566-26-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4,4,4-trimethyl-4-methylene-4l9-hepta-2,5-diyne
• CAS: 125566-26-9
• 化学式: C₄H₈Cl₂N₂O₂V
• 分子量: 237.967
• InChiKey: XGIUBSWFWUXOHE-UHFFFAOYSA-L

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：

  4,4,4-trimethyl-4-methylene-4l9-hepta-2,5-diyne 、 sodium tri(3,5-dimethyl-1-pyrazolyl)borohydride 以 乙腈 为溶剂， 以67%的产率得到(hydrotris(3,5-dimethyl-1-pyrazolyl)borate)V(O)(Cl)(NCMe)
  参考文献：
  名称：

  Inter- and Intramolecular Hydrogen-Bonding Interaction of Hydroxo Groups and Steric Effect of Alkyl Substituents on Pyrazolyl Rings in Tp^R Ligands:  Synthesis and Structural Characterization of Chloro-, Acetylacetonato-, and Hydroxo Complexes of VO²⁺ with Tp^Pri₂ and Tp^Me₂ Ligands

  摘要：

  Novel vanadyl (VO2+) chloro and hydroxo complexes with the hindered Tp(Pri2) (hydrotris(3,5-diisopropyl-1-pyrazolyl)borate) and Tp(Me2) (hydrotris(3,5-dimethylpyrazolyl-1-pyrazolyl)borate) ligands were prepared and structurally characterized successfully. Ligand displacement of VOCl2(MeCN)(2)(H2O) by Tp(R) afforded a series of octahedral chloro complexes, Tp(R)V(O)(Cl)(X) (1: R = Pr-2(i), X = Pz(Pri2)H; 2: R = Pri(2), X = py; 6: R = Me-2, X = NCMe). Hydrolysis of the obtained chloro complexes yielded the corresponding hydroxo complexes 4, 5, and 7, but their structures were very unique and different from that of the previously reported dinuclear VO2+ bis(mu-hydroxo) complex with the less hindered Tp(H2) (hydrotris(1-pyrazolyl)borate) ligand. For the Tp(Pri2) complexes, the octahedral hydroxo-aqua complex, Tp(Pri2)V(O)(OH)(OH2) (4), and the trinuclear bis(mu u-hydroxo)bis(mu-pyrazolato) complex, Tp(Pri2)V(O)(mu-OH)(mu-Pz(Pri2))V(O)(mu-OH)(mu-Pz(Pri2))V(O)Tp(Pri2) (5), were isolated. The hydroxo-aqua complex 4 was dimerized through the intermolecular hydrogen-bonding interaction between the hydroxo and aqua ligands forming the H3O2- bridging ligand. The trinuclear complex 5 consisted of two octahedral Tp(Pri2)V(O) fragments and a distorted trigonal-bipyramidal non-Tp(Pri2)-supported VO2+ center, sitting on the pseudo C-2 symmetry axis, and was formed via coupling of 4 and the VO2+-pyrazolato species, resulting from partial decomposition of the chloro complexes during the hydrolysis. Steric repulsion of the bulky Pr-i groups in Tp(Pri2) might hinder the formation of a dinuclear bis(mu u-hydroxo) complex like the Tp(H2) and Tp(Me2) derivatives. The dinuclear bis(mu-hydroxo) complex with the Tp(Me2) ligand, (kappa(3)-Tp(Me2))V(O)(mu-OH)(2)V(O)(kappa(2)-Tp(Me2)) (7), consisted of syn-arranged V=O fragments, having the different coordination geometries of the vanadium centers (octahedron with kappa(3)-Tp(Me2) and trigonal bipyramid with kappa(2)-Tp(Me2)). Intramolecular hydrogen-bending interaction between one of the two hydroxo groups and the noncoordinated pyrazolyl nitrogen atom in kappa(2)-Tp(Me2) was observed.

  DOI：

  10.1021/ic9806028
• 作为产物：
  描述：

  vanadyl(IV) chloride 在 SOCl₂ 作用下， 以 氯化亚砜 、 水 、 乙腈 为溶剂， 生成 4,4,4-trimethyl-4-methylene-4l9-hepta-2,5-diyne
  参考文献：
  名称：

  钒（IV）硫脲配合物的制备与表征：二氯双（1,3-二甲基咪唑烷-2-硫酮）-氧钒（IV）的晶体结构

  摘要：

  已经制备了新化合物[VOCl 2（MeCN）2（H 2 O）]，并通过元素分析，IR和ESR光谱进行了表征。该化合物是用于多种配合物的通用起始原料，特别是对于通式[VOCl 2 L 2 ]的配合物。为了说明[VOCl 2（MeCN）2（H 2 O）]的化学性质，制备了几种配合物，其中L = Ph 3PO，四甲基脲，咪唑烷-2-硫酮和1，3-二甲基咪唑烷-2-硫酮，并已通过元素分析对其进行了表征；紫外可见，红外和ESR光谱; 对于X ＝ 1，3-二甲基咪唑烷-2-硫酮（dmit），通过X射线晶体学测定。[VOCl 2（dmit）2 ]在正交空间群Pnn 2中结晶，其中a = 9.9684（6），b = 10.4631（9）和c = 8.5624（6），并且Z =2。该分子具有正方形金字塔形几何协调，与硫脲配体跨到对方。这是钒（IV）-硫脲配合物的晶体结构的第一个例子。

  DOI：

  10.1016/s0277-5387(00)86383-4

文献信息

• Collison, David; Eardley, David R.; Mabbs, Frank E., Inorganic Chemistry, 1993, vol. 32, # 5, p. 664 - 671
  作者：Collison, David、Eardley, David R.、Mabbs, Frank E.、Powell, Anne K.、Turner, Scott S.

  DOI：——

  日期：——