bis(tetrahydrofurane)oxovanadium(IV) dichloride | 53152-44-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: bis(tetrahydrofurane)oxovanadium(IV) dichloride
• CAS: 53152-44-6；29666-18-0；22512-00-1
• 化学式: C₈H₁₆Cl₂O₃V
• 分子量: 282.061
• InChiKey: FOISCUQEWHPGRZ-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：
  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：

  bis(tetrahydrofurane)oxovanadium(IV) dichloride 、 2-二甲氨基甲基-5-甲基-苯酚 在 Et₃N 作用下， 以 乙醚 为溶剂， 以77%的产率得到[VO(OC6H3(CH2NMe2)-2-Me-5)2]
  参考文献：
  名称：

  Synthesis and Characterization of O,N-Chelated Vanadium(IV) Oxo Phenolate Complexes:  Electronic Effect of Meta and Para Substituents on the Vanadium Center

  摘要：

  A series of O,N-chelated vanadium(IV) oxo bis(phenolate) complexes (1a-i) have been prepared from [VOCl2(THF)(2)] and several ortho-amino-functionalized phenols in the presence of a base. The intermediates in the synthesis of these compounds are mono(phenolato)vanadate complexes, as was shown by the reaction of [VOCl2(THF)(2)] with 1 equiv of HOC6H2(CH2NMe2)(2)-2,6-Me-4 in the absence of base. This yielded [VOCl2(OC6H2(CH2NMe2)2-Me-4-(CH2NHMe2)-6)] (2), in which the second amine function acts as an internal base, assisting in binding the formed equivalent of HCl. Complex 2 exists in the solid state as the dichlorovanadate(IV) species with the protonated amine function forming a three-centered intramolecular hydrogen bridge in which both a chloride atom and the oxygen atom of the phenolate ligand participate. EPR, UV-vis, and cyclic voltammetry analysis of the complexes with meta or para substituents (1a-g) on the aryloxy ring showed the hyperfine coupling constant, the HOMO-LUMO transition, and the oxidation potential, respectively, to be linearly related to the Hammett sigma constants of the substituents on the monoanionic aryloxy ring. The oxidation potential shows a large dependence (dE(ox)/d sigma = 170 mV (per phenoxy ligand)) on the Hammett constant. Crystal data: 1a, orthorombic, Pbca, a = 9.4321(7) Angstrom, b = 14.1919(14) Angstrom, c = 26.5484(14) Angstrom, V = 3553.8(5), Angstrom(3), Z = 8; 2, monoclinic, C2/c, a = 17.9977(15) Angstrom, b = 15.7445(9) Angstrom, c = 14.4986(6) Angstrom, beta = 113.206(5)degrees, V = 3776.0(4) Angstrom(3), Z = 4.

  DOI：

  10.1021/ic9901564
• 作为产物：
  描述：

  vanadia 、 氯 以 四氢呋喃 为溶剂， 生成 bis(tetrahydrofurane)oxovanadium(IV) dichloride
  参考文献：
  名称：

  Groshens, Thomas J.; Klabunde, Kenneth J., Inorganic Chemistry, 1990, vol. 29, # 16, p. 2979 - 2982

  摘要：

  DOI：
• 作为试剂：
  描述：

  苯乙醇 在 bis(tetrahydrofurane)oxovanadium(IV) dichloride 作用下， 以 二氯甲烷 为溶剂， 反应 12.5h， 以99%的产率得到乙酸苯乙酯
  参考文献：
  名称：

  Nucleophilic acyl substitutions of anhydrides catalyzed by oxometallic complexes

  摘要：

  本发明揭示了一种由氧化金属配合物催化的酰亲核取代（NAS）的无水酐方法。根据所述方法，酰亲核取代反应可以在氧化金属配合物的催化下发生，其中氧化金属配合物包括来自IVB、VB和VIB族的金属。

  公开号：

  US20060173213A1

文献信息

• Vanadium(IV and V) Complexes ContainingSNO (Dithiocarbonylhydrazone; Thiosemicarbazone) Donor Sets
  作者：Dongren Wang、Martin Ebel、Carola Schulzke、Cerstin Grüning、Saroj K. S. Hazari、Dieter Rehder

  DOI：10.1002/1099-0682(200104)2001:4<935::aid-ejic935>3.0.co;2-j

  日期：2001.4

  signals, two of which are due to two diastereomers. The EPR spectra of 3 and 4 in THF reveal the presence of octahedral species in solution. The crystal and molecular structures of complexes 3a·OCMe2, 5a, and 5b have been obtained, revealing basically a tetragonal pyramid, and coordination of the sulfur function in the thiocarbonyl (3) or enethiolate mode (5). The relevance of the compounds to bioinorganic

  VO2+ 复合物 [VOCl(ONS)] (3) 和 [VO(ONS)'] (4)，以及 VO3+ 复合物 [VO(OEt)(ONS)'] (5) ONS = (R)-水杨醛缩氨基硫脲(1-) R = 5,6-C4H4 (3a) 或 3-OMe (3b)；(ONS)' = (R)-水杨醛[benzylmercaptothiocarbonylhydrazonate(2−)], R = H, (4a/5a) 或 3-OMe (4b/5b)} 已制备并通过 IR、EPR、1H-、和 51V-NMR 光谱。在 (S)-sBuOH 中，4a 转化为 [VO(S)-OsBu}(ONS)'] (5c) 和 [VO(OH)(ONS)']（或其缩合产物）。5c 的溶液显示三个 51V NMR 信号，其中两个是由于两种非对映异构体。THF 中 3 和 4 的 EPR 光谱揭示了溶液中存在八面体物质。已获得
• Model Investigations of Vanadium−Protein Interactions:  Novel Vanadium(III) and Oxovanadium(IV) Compounds with the Diamidate Ligand 1,2-Bis(2-pyridinecarboxamide)benzene (H₂bpb)
  作者：Antonis T. Vlahos、Evagelos I. Tolis、Catherine P. Raptopoulou、Alexandros Tsohos、Michael P. Sigalas、Aris Terzis、Themistoklis A. Kabanos

  DOI：10.1021/ic990837z

  日期：2000.7.1

  Novel vanadium(III) and oxovanadium(IV) compounds with the diamidate ligand 1,2-bis(2-pyridinecarboxamide)benzene (H2bpb) were synthesized and structurally characterized. H2bpb is capable of binding to vanadium in either its anionic (dianionic-monoanionic) or its neutral form, resulting in complexes of various geometries and stoichiometries. The dianionic form (bpb2-), in NHEt3(trans-[VCl2(bpb)]) (1)

  合成了具有二氨基甲酸酯配体1,2-双（2-吡啶甲酰胺）苯（H2bpb）的新型钒（III）和氧钒（IV）化合物，并对其结构进行了表征。H2bpb能够以阴离子（双阴离子-单阴离子）或中性形式与钒结合，形成各种几何形状和化学计量的配合物。NHEt3（反式-[VCl2（bpb）））（1）和[VO（bpb）（H2O）] 05dmso036CH3OH013 （6x05dmsox036CH3OHx013 ）中的双阴离子形式（bpb2-）充当平面四齿双[N-氨基甲酸酯-N -吡啶]赤道配体。单阴离子形式（Hbpb-）在[V（Hbpb）3] 2CHCl3（22CHCl3）和mu 2-bridged-eta 4-（Npy，Oam）中表现为（Npy，Oam）或（Npy，Nam）螯合剂[VOCl（Hbpb）]（2）x2CH3NO2（3x2CH3NO2）中的-Npy，Nam），而中性的H2bpb则表现为mu
• Thio‐Ligation to Vanadium: The <i>NSSN</i> and <i>S′N′O</i> Donor Sets (N = Pyridine, N′ = Enamine; S = Thioether, S′ = Thiolate)
  作者：Mahin Farahbakhsh、Henning Nekola、Häke Schmidt、Dieter Rehder

  DOI：10.1002/cber.19971300815

  日期：1997.8

  yields the non-oxo V′” complex [V(S′N′O)2] 2, derived from the Schiff base HS′N′OH, where 0 and S′ are phenolate and thiophenolate functions, respectively, and N′ is the Schiff base (enamine) nitrogen. Complex 2, with the ligands in a distorted trigonal-antiprismatic array, is a rare example of a structurally characterized complex where the Schiff base is preserved at the expense of its thiazoline tautomeric

  四齿，中性二硫化物[双（硫醚）]配体1,6-双（ø -吡啶基）-2,4- dithiahexane，NSSN，与发生反应[VCI 2（TMEDA）2 ]，以形成八面体（清一色顺式; ç 2V -对称）配合物[的VCl 2（NSSN）] 1，第一低价的钒配合物，其中所述硫代功能是只有机硫化物。用邻巯基苯胺处理（VOCl 2（thf）2 ] ，然后与邻羟基萘乙醛反应，生成非羰基V'''络合物[V（S'N'O）2 ] 2衍生自席夫碱HS'N'OH，其中0和S'分别为酚盐和硫酚盐官能团，而N'为席夫碱（烯胺）氮。复杂2，在畸变三角-反棱柱阵列的配位体，是一种罕见的示例的，其中席夫碱在其噻唑啉的互变异构形式的代价保存了结构表征复杂。
• Unexpected reduction of vanadium(IV) to vanadium(III) in the presence of the chelate ligands 2,2′-bipyridine (bpy) and 1,8-hydroxyquinoline (Hquin)
  作者：Manolis J. Manos、Anastasios J. Tasiopoulos、Catherine Raptopoulou、Aris Terzis、J. Derek Woollins、Alexandra M. Z. Slawin、Anastasios D. Keramidas、Themistoklis A. Kabanos

  DOI：10.1039/b102095l

  日期：——

  The structures, NMR spectra and electrochemical properties of the vanadium(III) compounds, cis-[VIIICl2(acac)(bpy)] and [VIII(quin)3]·2CH3OH, formed from [VIVCl2(acac)2]·0.25CH2Cl2 (Hacac = pentane-2,4-dione) and [VIVOCl2(thf)2] with bpy and Hquin respectively are described as well as the structure of the catecholate dioxovanadium(V) dimer [Et3NH]2[VO2(μ-dtbc)]2 (H2dtbc = 3,5-di-tert-butylcatechol)

  结构， 核磁共振谱和钒（电化学性能III）的化合物，顺式- [V III氯2（ACAC）（联吡啶）]和[V III（五重峰）3 ]·2CH 3 OH，从[V形成IV氯2（ACAC）2 ]·0.25CH 2 Cl 2（HaCAC = 戊烷-2,4-二酮）和[V IV OCl 2（thf ）2 ]与py分别描述了Hquin和Hquin，以及儿茶酚二氧钒（V）二聚体[Et 3 NH] 2 [VO 2（μ-dtbc）] 2（H 2 dtbc =3,5-二叔丁基邻苯二酚）。
• Monomeric Oxovanadium(IV) Compounds of the General Formula <i>cis</i>-[V^IV(O)(X)(L_NN)₂]^+/0 {X = OH^-, Cl^-, SO₄²^- and L_NN = 2,2‘-Bipyridine (Bipy) or 4,4‘-Disubstituted Bipy}
  作者：Georgios D. Triantafillou、Evagelos I. Tolis、Aris Terzis、Yiannis Deligiannakis、Catherine P. Raptopoulou、Michael P. Sigalas、Themistoklis A. Kabanos

  DOI：10.1021/ic034440d

  日期：2004.1.1

  [V(IV)OCl(2)(THF)(2)] in ethanol with 2 equiv of bipy gives the compounds cis-[V(IV)O(OSO(3))(bipy)(2)].CH(3)OH.1.5H(2)O (6.CH(3)OH.1.5H(2)O) and cis-[V(IV)OCl(bipy)(2)]Cl (7), respectively, while reaction of 1 equiv of [V(IV)OCl(2)(THF)(2)] in CH(2)Cl(2) with 2 equiv of 4,4'-dtbipy gives the compound cis-[V(IV)OCl(4,4'-dtbipy)(2)]Cl.0.5CH(2)Cl(2) (8.0.5CH(2)Cl(2)). Compounds cis-[V(IV)O(BF(4))(4,4'-dtbipy)(2)]BF(4)

  [V（IV）OCl（2）（THF）（2）]在水溶液中与2当量的AgBF（4）或AgSbF（6）反应，然后与2当量的2,2'-联吡啶（bipy）反应， 4,4'-二叔丁基-2,2'-联吡啶（4,4'-dtbipy）或4,4'-二甲基-2,2'-联吡啶（4,4'-dmbipy）得到通式cis- [V（IV）O（OH）（L（NN））（2）] Y的化合物[其中L（NN）= bipy，Y = BF（4）（-）（1）， L（NN）= 4,4'-dtbipy，Y = BF（4）（-）（2.1.2H（2）O），L（NN）= 4,4'-dmbipy，Y = BF（4）（ -）（3.2H（2）O），并且L（NN）= 4,4'-dtbipy，Y = SbF（6）（-）（4）]。依次向包含1当量V（IV）OSO（4）.5H（2）O的水溶液中依次添加1当量Ba（ClO（4））（2），然后再添加2当量Bipy。 （IV）O（OH）（联吡啶）（2）]