NbF5(1,4-dioxane) | 1191449-30-5

• 英文名称: NbF5(1,4-dioxane)
• CAS: 1191449-30-5
• 化学式: C₄H₈F₅NbO₂
• 分子量: 276.005
• InChiKey: ADHIMDCBPOWOOA-UHFFFAOYSA-I

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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  1,4-二氧六环 、 氟化铌(V) 以 二氯甲烷 为溶剂， 以83%的产率得到NbF5(1,4-dioxane)
  参考文献：
  名称：

  通过与铌和五卤化钽配位而促进的通过CO键断裂的含氧分子的断裂。

  摘要：

  新型mu-oxo配合物NbOX（3）[kappa（2）-O（Me）CH（2）CO（2）Me] NbX（5）（X = Cl，; X = Br，），NbOCl（3） [kappa（2）-（MeO（2）C）CH [双键，长度为m-破折号] CH（CO（2）Me）] NbCl（5）（）和NbOCl（3）[kappa（2）- CH（2）（CO（2）Me）（2）] NbCl（5）（）已通过卤化物NbX（5）（X = Cl，Br）与甲氧基甲基的摩尔比为1：1的反应以高收率制备乙酸盐[MeOCH（2）CO（2）Me]，马来酸二甲酯[（MeO（2）C）CH [双键，长度为m-dash] CH（CO（2）Me）]和丙二酸二甲酯[CH（2 ）（CO（2）Me）（2）]，分别在不同的实验条件下进行。NMR研究表明，和的氧代单元通过选择性断裂（CO键断裂）形成一半当量的有机材料。离子络合物[NbX（4）{OO}（2）]

  DOI：

  10.1039/b905023j

文献信息

• Structures and Unusual Rearrangements of Coordination Adducts of MX₅ (M = Nb, Ta; X = F, Cl) with Simple Diethers. A Crystallographic, Spectroscopic, and Computational Study
  作者：Riccardo Bini、Cinzia Chiappe、Fabio Marchetti、Guido Pampaloni、Stefano Zacchini

  DOI：10.1021/ic9020806

  日期：2010.1.4

  High-yield reactions of the pentafluoride complexes MF5 (M=Nb, Ta) with a variety of diethers, ROCH2CH(R')OR '', afford the ionic derivatives [MF4kappa(2)-ROCH2CH(R')OR ''}(2)][MF6] (2a-2e) or [MF4ROCH2CH(R')OR ''}(2)][M2F11] (3a-3f) according to the metal/diether ratio employed, The structures of [MF4(kappa(2)-dme)(2)][MF6] [M=Nb (2a), Ta (2b); dme=MeOCH2CH2OMe] have been determined by X-ray diffraction. Moreover, the structure of the cationic part of 2a in the gas phase has been optimized by density functional theory calculations (the B3LYP/LANL2DZ method). An analogous computational study has allowed one to predict the existence of a heptacoordinated niobium cation within the species [NbCl4(dme)(2)][NbCl6]. This prediction has been confirmed by NMR identification at -60 degrees C of the complexes [MCl4(kappa(2)-dme)(kappa(1)-dme)][MCl6] [M=Nb (4a), Ta (4b)], obtained by the addition of dme to MCl5 in CDCl3. Activation of the coordinated diether in 2 and 3 takes place in solution at high temperature and generally proceeds via cleavage of C-O bonds and coupling of the fragments produced. Thus, OR2 (R=Me, Et) and 1,4-dioxane have been obtained selectively upon thermal reaction of MF5 with dme, diglyme, or 1,2-diethoxyethane, followed by treatment with water. In analogous conditions, 1,2-dimethoxypropane converts mainly into acetone and dimethyl ether. The formation of dioxane from dme occurs in high yield also by using a catalytic amount of NbF5. The activation of dme by NbF5 follows a pathway different from that previously reported for NbCl5, and an explanation based on the thermodynamic parameters calculated at the B3LYP/LANL2DZ level is given: the formation of Me2O and dioxane is the most favored reaction between NbF5 and dme (Delta G(r)degrees = -15.16 kcal . mol(Nb)(-1)), while the formation of MeCl and dioxane is the most favored reaction in the case of NbCl5/dme (Delta G(r)degrees = -53.13 kcal . mol(Nb)(-1)).