HfCl4(tetrahydrothiophene)2 | 21959-06-8

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: HfCl4(tetrahydrothiophene)2
• 英文别名: HfCl4(THT)2；tetrachlorohafnium;thiolane
• CAS: 21959-06-8
• 化学式: C₈H₁₆Cl₄HfS₂
• 分子量: 496.649
• InChiKey: XSMLBFDNRWOSNM-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：

  HfCl4(tetrahydrothiophene)2 、 dilithium;bis[(dimethylamino)methyl-dimethylsilyl]azanide 以 乙醚 为溶剂， 以89%的产率得到
  参考文献：
  名称：

  新型酰胺化锂配体前体的合成和结构：分子式为N（SiMe（2）CH（2）NMe（2））（2）的三齿氮基供体。合成和结构的第4组酰胺MCl（3）[N（SiMe（2）CH（2）NMe（2））（2）]（M = Ti，Zr，Hf）。

  摘要：

  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。

  DOI：

  10.1021/ic970168u
• 作为产物：
  描述：

  四氢噻吩 、 氯化铪 以 二氯甲烷 为溶剂， 生成 HfCl4(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 the Hafnium Alkylidene Complex [P₂Cp]HfCHPh(Cl) ([P₂Cp] = (η⁵-C₅H₃-1,3-(SiMe₂CH₂PPrⁱ₂)₂))
  作者：Michael D. Fryzuk、Paul B. Duval、Brian O. Patrick、Steven J. Rettig

  DOI：10.1021/om000760i

  日期：2001.4.1

  The synthesis, structural characterization, and solution behavior of hafnium complexes stabilized by the potentially tridentate ancillary ligand [P2Cp] ([P2Cp] = (η5-C5H3-1,3-(SiMe2CH2PPri2)2)) are described. The reaction of [P2Cp]Li with HfCl4(THT)2 produces the hafnium trichloride complex [P2Cp]HfCl3 (1), the structure of which was determined by X-ray crystallography. Trichloride 1 is isostructural

  的合成，结构表征，以及由三齿潜在辅助配体[P稳定铪配合物的溶液行为2的Cp]（[P 2的Cp] =（η 5 -C 5 H ^ 3 -1,3-（森达2 CH 2 PPR描述i 2）2））。[P 2 Cp] Li与HfCl 4（THT）2的反应产生三氯化ha配合物[P 2 Cp] HfCl 3（1），其结构通过X射线晶体学测定。三氯化物1是类似的结构，具有类似的锆络合物[P 2 Cp] ZrCl 3（2），呈固态，但在溶液1中以两种异构体的平衡混合物形式存在，该两种异构体通过通量膦配位而相互转化。用2当量的KCH 2 Ph处理1，然后进行热分解，得到第一个结构上表征的alkyl亚烷基络合物[P 2 Cp] Hf CHPh（Cl）（3）。对3的晶体结构测定表明，该配合物与锆类似物[P 2 Cp] Zr CHR（Cl）是同构的（4）。此处介绍的Hf系统与先前研究的Zr类似物之间的主要区别在于，前者