ZrCl4(tetrahydrothiophene)2 | 21959-02-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻嗪类
• 英文名称: ZrCl4(tetrahydrothiophene)2
• 英文别名: ZrCl4(THT)2；tetrachlorozirconium;thiolane
• CAS: 21959-02-4
• 化学式: C₈H₁₆Cl₄S₂Zr
• 分子量: 409.383
• InChiKey: YKBRHPUAYQAVGA-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  5.78
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [PhAs(CH2SiMe2NSiMe2CH2)2AsPh]Li2(1,4-dioxane) 、 ZrCl4(tetrahydrothiophene)2 以 甲苯 为溶剂， 以70%的产率得到[PhAs(CH2SiMe2NSiMe2CH2)2AsPh]ZrCl2
  参考文献：
  名称：

  含砷供体的大环配体的合成，表征和配位化学。

  摘要：

  介绍了大环二酰胺基-二氮杂配体[As2N2] Li2（1,4-二恶烷）（1）（其中As2N2 = PhAs（CH2SiMe2NSiMe2CH2）2AsPh）的制备和表征，以及一系列早期过渡金属配合物。配合物[As2N2] MCl2（M = Zr，2; Ti，4）和配合物（[As2N2] Y）2（mu-Cl）2（5）可以通过1与相应的THF THF加成反应制备金属卤化物。2，[As2N2] ZrI2（3）的碘化物衍生物可通过与碘代三甲基硅烷反应制备。锂络合物1显示出非常长的锂-砷键距离为3.162（10）A，并且钇络合物5是第一个已知的含有钇-砷键的络合物。用C8K或活化的镁还原2、3或4，以使配体与金属中心分离的方式分解配合物。

  DOI：

  10.1039/b415976d
• 作为产物：
  描述：

  四氢噻吩 、 氯化锆(IV) 以 二氯甲烷 为溶剂， 生成 ZrCl4(tetrahydrothiophene)2
  参考文献：
  名称：

  锆（IV）和ha（IV）夹心卟啉配合物的光谱表征

  摘要：

  Optical, infrared (IR), and resonance Raman (RR) spectra are reported for the sandwich porphyrins Zr(OEP)2 and Hf(OEP)2 (OEP = octaethylporphyrin) and their respective mono- and dication radicals. For comparison, absorption and vibrational data were also obtained for representative neutral and oxidized monomeric Zr(IV) and Hf(IV) complexes. The vibrational data for both the monocations (all complexes) and dications (sandwich complexes only) indicate that the electrons are removed from an a1u-like molecular orbital. Consequently the ground states of the singly and doubly oxidized compounds are 2A1u and 1A1g, respectively. The C(b)C(b) stretching vibrations are found to be the most reliable indicators of oxidation. These modes exhibit almost linear upshifts upon successive oxidations of the porphyrin rings. On the basis of the shift-pattern exhibited by the IR oxidation-marker bands of the Zr(IV) and Hf(IV) species, the oxidation-marker band of MOEP complexes is identified as the nu38 (C(b)C(b)) stretching mode. In the course of the RR studies of the sandwich complexes, experiments were performed in which the excitation energy is resonant with the new electronic states that arise due to the strong pipi interactions in these assemblies. These include the Q' and Q'' states of the neutral species and the near-IR charge-resonance states of the cations. No RR scattering is observed upon excitation into either the Q' or Q'' absorptions. In contrast, excitation into the near-IR absorptions of the mono- and dications results in RR scattering from out-of-plane deformations of the porphyrin rings. The resonance enhanced out-of-plane deformations appear to be symmetrical linear combinations of porphyrin monomer vibrations rather than intradimer vibrations (modes that arise due to the additional degrees of freedom present in the dimer versus the two independent monomers). Collectively, the studies of the neutral and oxidized M(OEP)2 complexes provide further insights into the effects of strong pipi interactions and the consequences of ring-based oxidations in porphyrinic systems.

  DOI：

  10.1021/j100109a014

文献信息

• Synthesis and Structure of Zirconium(IV) Complexes Stabilized by the Bis(amido−phosphine) Macrocycle [P₂N₂] {[P₂N₂] = PhP(CH₂SiMe₂NSiMe₂CH₂)₂PPh}
  作者：Michael D. Fryzuk、Jason B. Love、Steven J. Rettig

  DOI：10.1021/om9707984

  日期：1998.3.1

  The preparation and characterization of a series of zirconium(IV) complexes that incorporate the macrocyclic bis(amido−phosphine) ligand PhP(CH2SiMe2NSiMe2CH2)2PPh, [P2N2], are described. The starting material, ZrCl2[P2N2], is prepared by reaction of syn-Li2(S)[P2N2] (S = dioxane or THF) with ZrCl4L2 (L = THT, tetrahydrothiophene; L = THF, tetrahydrofuran). Subsequent replacement of the chloride ligands

  描述了一系列结合了大环双（氨基-膦）配体PhP（CH 2 SiMe 2 NSiMe 2 CH 2）2 PPh [P 2 N 2 ]的锆（IV）配合物的制备和表征。通过合成-Li 2（S）[P 2 N 2 ]（S =二恶烷或THF）与ZrCl 4 L 2反应制备原料ZrCl 2 [P 2 N 2 ]（L ＝ THT，四氢噻吩； L ＝ THF，四氢呋喃）。可以随后替换氯化物配体以生成二烷基络合物ZrR 2 [P 2 N 2 ]（R = Me，CH 2 Ph）。用“镁丁二烯”反应，镁（C 4 H ^ 6）·2THF，导致π-η的形成4丁二烯复杂的Zr（η 4 -C 4 H ^ 6）[P 2 Ñ 2 ]。另外，可以通过添加LiNHBu t来制备叔丁基亚氨基配合物Zr（NBu t）[P 2 N 2 ]。ZrCl 2 [P 2 N 2 ]。通过X射线晶体学对许多上述配合物进行了表征，所有这些配合物均
• (Alkyliminomethyl)phenylamido and related complexes of zirconium and titanium
  作者：Robin M. Porter、Scott Winston、Andreas A. Danopoulos、Michael B. Hursthouse

  DOI：10.1039/b202471c

  日期：——

  A range of trialkylsilylamido complexes of zirconium in which the silylamido functional group is attached to an o-(alkyliminomethyl)- or an o-(alkyliminoethyl)-substituted aromatic ring have been synthesised by salt elimination or aminolysis reactions and characterised by spectroscopic and diffraction methods. The monoanionic ligands (L), formally isoelectronic to the cyclopentadienyl ligand, can be introduced to zirconium by reaction of LLi with ZrCl4 under a variety of conditions giving rise to complexes of type LZrCl3 and L2ZrCl2, by reaction of LLi with Zr(NMe2)2Cl2(THF)2, and Zr(NEt2)2Cl2(THF)2 giving rise to LZrCl(NMe2)2Cl and LZrCl(NEt2)2Cl, respectively, or by reaction of LH with Zr(NMe2)4 giving rise to LZr(NMe2)3. LZr(NMe2)2Cl and LZr(NEt2)2Cl can be transformed to LZrCl3 by reaction with Me3SiCl, while LZr(NMe2)3 on heating rearranges to dimeric imido complexes by elimination of amidosilanes. Aminolysis of Zr(NMe2)2Cl2(THF)2 with LH results in a formal insertion of the imino CN into the Zr-amido bond. The combination of enolisable imine and a bulky silyl amide gave rise to a new mixed donor ligand system comprising of one silylamido and one eneamido group. Finally aminolysis of Ti(NMe2)Cl2 with LH resulted in the isolation of a C3 symmetric triamido titanium complex.

  已合成一系列三烷基硅氨基锆配合物，其中硅氨基官能团连接到o-(烷基亚氨基甲基)或o-(烷基亚氨基乙基)取代芳香环上，并通过盐消除或氨解反应进行表征，采用光谱和衍射方法进行分析。这些单负离子配体(L)形式上等电子于环戊二烯配体，可以通过在各种条件下将LLi与ZrCl4反应引入锆，生成LZrCl3和L2ZrCL2类型的配合物，或者通过将LLi与Zr(NMe2)2CL2(THF)2及Zr(NEt2)2CL2(THF)2反应，分别得到LZrCl(NMe2)2Cl和LZrCl(NEt2)2Cl，或通过将LH与Zr(NMe2)4反应生成LZr(NMe2)3。LZr(NMe2)2Cl和LZr(NEt2)2Cl可以通过与Me3SiCl反应转化为LZrCl3，而LZr(NMe2)3在加热时通过消除氨基硅烷重排为二聚亚胺配合物。将Zr(NMe2)2CL2(THF)2与LH进行氨解反应会导致亚胺CN正式嵌入Zr-氨基键中。可酮化的亚胺与庞大的硅氨基的组合产生了一种新的混合供体配体系统，包含一个硅氨基和一个烯氨基。最后，将Ti(NMe2)CL2与LH进行氨解反应，成功分离出了一种C3对称的三氨基钛配合物。
• Indenyl- and Fluorenyl-Functionalized N-Heterocyclic Carbene Complexes of Titanium, Zirconium, Vanadium, Chromium, and Yttrium
  作者：Stephen P. Downing、Susana Conde Guadaño、David Pugh、Andreas A. Danopoulos、Ronan M. Bellabarba、Martin Hanton、David Smith、Robert P. Tooze

  DOI：10.1021/om700269u

  日期：2007.7.1

  Dimethylindenyl-functionalized N-heterocyclic carbene complexes of titanium(IV), titanium(III), zirconium(IV), and vanadium(III) were prepared from potassium indenylcarbenes by salt elimination reactions. X-ray diffraction studies revealed that in the complexes the ligand adopts a bidentate coordination mode. Alkanolysis of a dimethylindene-functionalized imidazolium salt with Y(CH2SiMe3)3(THF)2 gave

  钛（IV），钛（III），锆（IV）和钒（III）的二甲基茚基官能化的N-杂环卡宾配合物是通过盐消除反应从茚基卡宾钾制备的。X射线衍射研究表明，在配合物中，配体采用双齿配位模式。用Y（CH 2 SiMe 3）3（THF）2进行二甲基茚基官能化的咪唑鎓盐的碱解反应，生成了二聚溴化钇烷基，其中配体采用了双齿共氧化方式。芴官能化的咪唑鎓盐与[Cr（N（SiMe 3）2）2（THF）2）的氨解}生成了铬（II）络合物，其中配体通过带有悬垂芴基的N-杂环卡宾末端采用单齿结合模式。
• Synthesis and Structure of a New Lithium Amide Ligand Precursor:  A Tridentate Nitrogen-Based Donor Set of the Formula N(SiMe₂CH₂NMe₂)₂. Synthesis and Structure of the Group 4 Amides MCl₃[N(SiMe₂CH₂NMe₂)₂] (M = Ti, Zr, Hf)
  作者：Michael D. Fryzuk、Vera Hoffman、James E. Kickham、Steven J. Rettig、Sandro Gambarotta

  DOI：10.1021/ic970168u

  日期：1997.7.1

  The new lithium amide LiN(SiMe(2)CH(2)NMe(2))(2) was prepared by reaction of NH(3) with the corresponding silylamine Me(2)NSiMe(2)CH(2)NMe(2) followed by addition of butyllithium. This lithium derivative exists as a dimer in the solid state wherein the two lithium ions are bridged by the two amido units with the amine arms of each unit bonded to opposite lithium centers in an overall pseudo D(2) structure;

  通过使NH（3）与相应的甲硅烷基胺Me（2）NSiMe（2）CH（2）NMe（2）反应制备新的氨基酰胺锂LiN（SiMe（2）CH（2）NMe（2））（2） ），然后加入丁基锂。该锂衍生物以二聚体的形式存在，其中两个锂离子被两个酰胺单元桥接，每个单元的胺臂在整个拟D（2）结构中与相对的锂中心键合；然而，在溶液中，助熔过程用于使二聚体单元的对映体形式相互转化。已经研究了酰胺化锂二聚体的配位化学。与一系列第4组起始卤化物MCl（4）反应，生成相应的配合物MCl（3）[N（SiMe（2）CH（2）NMe（2））（2）]，其中M = Ti， Zr和Hf。介绍了这些起始三卤化物在溶液和固态下的结构。
• η²-Sulfenamido and -selenamido complexes of titanium, zirconium, molybdenum and tungsten
  作者：Danielle M. Hankin、Andreas A. Danopoulos、Geoffrey Wilkinson、Tracy K. N. Sweet、Michael B. Hursthouse

  DOI：10.1039/dt9960001309

  日期：——

  The interaction of TiCl4 with LiN(Bu(t))SR (R = Ph or C(6)H(2)Me(3)-2,4,6) gave the sulfenamido complexes TiCl2(eta(2)-Bu(t)NSR)(2). Interaction of ZrCl4 with 3 equivalents of LiN(Bu(t))SPh produced ZrCl(eta(2)-Bu(t)NSPh)(3) while ZrCl4(tht)(2) (tht = tetrahydrothiophene) with 5 equivalents gave the homoleptic Zr(eta(2)-Bu(t)NSPh)(4). From ZrCl2(eta(5)-C5H5)(2) only ZrCl(eta(5)-C5H5)(2)(eta(2)-Bu(t)NSPh) 5 is obtained. Using as starting materials MO(2)Cl(2)(dme) (dme = 1,2-dimethoxyethane, M = Mo or W), MoCl2(NBu(t))(2) and WCl2(NBu(t))(2)(py)(2) (py = pyridine), interactions with LiNBu(t)SPh gave eta(2)-sulfenamido compounds such as MoO2(eta(2)-Bu(t)NSPh)(2). The selenium analogue of the tungsten compound, i.e. W(NBu(t))(2)(eta(2)-Bu(t)NSePh)(2) has been made by interaction of Li2W(NBu(t))(4) with PhSeBr. Where study was possible, NMR spectra over a temperature range indicate that invertomers and isomers occur. Six compounds have been structurally characterised by X-ray diffraction. In all cases the sulfenamido ligands are eta(2) bonded and the geometry about the N atoms is planar.