{NbCl₂(tetrahydrothiophene)}₂(μ-Cl)₂(μ-tetrahydrothiophene) | 38531-73-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻烷
• 英文名称: {NbCl₂(tetrahydrothiophene)}₂(μ-Cl)₂(μ-tetrahydrothiophene)
• 英文别名: {NbCl₂(THT)}₂(μ-Cl)₂(μ-THT)；[(NbCl2(tetrahydrothiophene))2(μ-Cl)2(μ-tetrahydrothiophene)]；[(NbCl2(THT))2(μ-Cl)2(μ-THT)]；Nb2Cl6(THT)3
• CAS: 38531-73-6
• 化学式: C₁₂H₂₄Cl₆Nb₂S₃
• 分子量: 663.051
• InChiKey: UVSFTXHHWDSHBD-UHFFFAOYSA-J

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：

  {NbCl₂(tetrahydrothiophene)}₂(μ-Cl)₂(μ-tetrahydrothiophene) 在 H₂SO₄ 、 (NH₄)2SO₄ 作用下， 以 四氢呋喃 、 水 为溶剂， 以64%的产率得到(NH4)3(H3O)2{Nb3(μ3-O)2(SO4)6(H2O)3}*nH2O
  参考文献：
  名称：

  氧代三核金属-金属键合铌化合物的新化学

  摘要：

  Nb 2 Cl 6（四氢噻吩）3与含水酸的反应提供了通向羰基三核金属-金属键合物质的一般途径，例如[Nb 3（µ 3 -O）2（SO 4）6（H 2 O）3 ] 5–，[Nb 3（µ 3 -O）2（O 2 CMe）6（四氢呋喃）3 ] +和[Nb 3（µ 3 -S）（µ 2 -O）3（NCS）9 ]6 –。

  DOI：

  10.1039/c39860001276
• 作为产物：
  描述：

  四氢噻吩 、 {NbCl₂(dimethyl sulfide)}₂(μ-Cl)₂(μ-dimethyl sulfide) 以 二氯甲烷 为溶剂， 以80%的产率得到{NbCl₂(tetrahydrothiophene)}₂(μ-Cl)₂(μ-tetrahydrothiophene)
  参考文献：
  名称：

  Dinuclear Niobium(III) Complexes [{NbCl₂(L)}₂(μ-Cl)₂(μ-L)] (L = tetrahydrothiophene, dimethyl sulfide):  Preparation, Molecular Structures, and the Catalytic Activity for the Regioselective Cyclotrimerization of Alkynes

  摘要：

  Dinuclear niobium complexes [ {NbCl2L}(2)( mu-Cl)(2)( mu-L)] ( L) tetrahydrothiophene C4H8S, THT ( 1a)) have been prepared by the reaction of diniobium( V) decachloride ( Nb2Cl10) with magnesium in THT. The structure of 1a was determined by X-ray crystallography to have a Nb-Nb bond, which is consistent with that of 1b ( L) dimethyl sulfide, Me2S). The reaction of 1a, as well as 1b, with alkyne ( R1C CR2) at room temperature gave a head-to-tail cycloadded alkyne trimer, 1,3,5-( R-1)(3)-2,4,6-( R-2)(3)-benzene ( R-1) H, R-2) Ph ( 2); R-1) p-tolyl, R-2) H ( 3); R-1) R-2) CH2Cl ( 4); R-1) R-2) COOEt ( 5); R-1) n-Pr, R-2) Me ( 6); R-1) n-Bu, R-2) H ( 7); R-1) Me3Si, R-2) H ( 8), R-1) R-2) Et ( 9), R-1) R-2) n-Pr ( 10)), regioselectively in high yields. The cyclotrimerization is found to be catalyzed by complexes 1a and 1b, since only 1/600 equiv of the complex to the alkynes can lead to the corresponding product in high yields. The reactions of 1a with 6 equiv of 3-hexyne and 4-octyne gave a mononuclear byproduct, NbCl3( eta(2)-RC CR-RC=CR) ( R) Et ( 11), Pr ( 12)), besides 9 and 10, respectively. The reactions of 11 or 12 with an excess of original alkyne, however, resulted exclusively in the formation of the corresponding benzene derivative, in equimolar amount to 1,2,3,4-( R) 4- 5,6-( R')(2)-benzene ( R) R') Et ( 9), R) R') Pr ( 10), R) Et, R') Pr ( 13), R) n-Pr, R') Et ( 14)). This observation suggests that the mononuclear species does not behave as a catalyst, and the regioselectivity may be due to a dinuclear structure of the niobium complexes.

  DOI：

  10.1021/om0601100

文献信息

• Dinuclear niobium(III) and tantalum(III) complexes with thioether and selenoether ligands [{MIIIX2(L)}2(μ-X)2(μ-L)] (M = Nb, Ta; X = Cl, Br; L = R2S, R2Se): Syntheses, structures, and the optimal conditions and the mechanism of the catalysis for regioselective cyclotrimerization of alkynes
  作者：Masatoshi Matsuura、Takashi Fujihara、Masaki Kakeya、Tomoaki Sugaya、Akira Nagasawa

  DOI：10.1016/j.jorganchem.2013.07.035

  日期：2013.11

  catalytic activity. The niobium(III) chloride complexes with selenoether (L = dimethyl selenide (Me2Se), tetrahydroselenophene (C4H8Se, THSe, selenolane) have higher rates for the reaction with alkynes, but low activity for the cyclotrimerization. Tantalum(III) chloride complexes (L = Me2S, THT, tetrahydrothiopyran (C5H10S, THTP, thiane)) have lower catalytic activities than the niobium(III) ones, because

  一系列具有硫属元素供体[M III X 2（L）} 2（μ-X）2（μ-L）]的双核卤化铌（III）和钽（III）络合物（M = Nb; X = Cl， Br; L = R 2 S，R 2 Se）（M = Ta; X = Cl，Br; L = R 2 S）已通过二金属（V）十卤化物（M 2 X 10）和镁和L。通过X射线晶体学测定，其中五个新配合物的结构具有MM双键。事实证明，溶剂和温度在实现炔烃的环三聚化的高产率和区域选择性中起重要作用。氯化铌（III）配合物（L =二甲基硫醚（Me 2 S），四氢噻吩（C 4 H 8 S，THT，噻吩）在室温下在甲苯中与苯乙炔反应，得到了首尾相接的三环三聚体炔，1,3,5- （Ph）3 -2,4,6-（H）3-苯和头对头环加成的1,2,4-（Ph）3 -3,5,6- （高）3-苯，收率高。硫醚配体越小，催化活性越高。氯化铌与硒醚（L =二甲基硒化物（Me
• Gilletti; Femec; Keen, Inorganic Chemistry, 1992, vol. 31, # 19, p. 4008 - 4012
  作者：Gilletti、Femec、Keen、Brown

  DOI：——

  日期：——
• Cotton, F. Albert; Diebold, Michael P.; Roth, Wieslaw J., Inorganic Chemistry, 1988, vol. 27, # 13, p. 2347 - 2352
  作者：Cotton, F. Albert、Diebold, Michael P.、Roth, Wieslaw J.

  DOI：——

  日期：——
• Cotton, F. Albert; Diebold, Michael P.; Roth, Wieslaw J., Inorganic Chemistry, 1985, vol. 24, # 22, p. 3509 - 3510
  作者：Cotton, F. Albert、Diebold, Michael P.、Roth, Wieslaw J.

  DOI：——

  日期：——
• Synthesis and characterization of niobium(III) and tantalum(III) dimers with bidentate ligands
  作者：M.E. Clay、T.M. Brown

  DOI：10.1016/s0020-1693(00)81698-9

  日期：1983.1