(η5-C5Me5)Hf(CH3)3 | 113161-86-7

• 英文名称: (η5-C5Me5)Hf(CH3)3
• 英文别名: Cp'HfMe3；(η⁵-C5Me5)Hf(CH3)3；[(1,2,3,4,5-pentamethylcyclopentadienyl)HfMe3]；Cp(*)HfMe3；[Cp*HfMe3]；Cp*HfMe3
• CAS: 113161-86-7
• 化学式: C₁₃H₂₄Hf
• 分子量: 358.824
• InChiKey: TYUCARUVBABIHJ-UHFFFAOYSA-N

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：

  (η5-C5Me5)Hf(CH3)3 在 H₂ 作用下， 以 甲苯 为溶剂， 生成 methane
  参考文献：
  名称：

  第4组金属多金属氢化物：四（五甲基环戊二烯基氯化二ha）的合成，结构和反应活性

  摘要：

  DOI：

  10.1021/om00095a003
• 作为产物：
  描述：

  甲基溴化镁 在 (Cp'HfCl₃)x 作用下， 以 乙醚 为溶剂， 以86%的产率得到(η5-C5Me5)Hf(CH3)3
  参考文献：
  名称：

  Organometallic thermochemistry. Metal hydrocarbyl, hydride, halide, carbonyl, amide, and alkoxide bond enthalpy relationships and their implications in pentamethylcyclopentadienyl and cyclopentadienyl complexes of zirconium and hafnium

  摘要：

  DOI：

  10.1021/ja00231a020

文献信息

• Propylene Polymerization with Cyclopentadienyltitanium(IV) Hydroxylaminato Complexes
  作者：Andrew P. Dove、Elizabeth T. Kiesewetter、Xavier Ottenwaelder、Robert M. Waymouth

  DOI：10.1021/om800571j

  日期：2009.1.26

  PhOMe. Cp*Ti(Me)2(ONtBu(Me)) was revealed to be a weaker donor than Cp*Ti(Me)2(ONEt2); Cp*Ti(Me)2(TEMPO) did not bind to AlMe3. AliBu3 bound more weakly to Cp*Ti(Me)2(ONEt2) than AlMe3. Reaction of Cp*Ti(Me)2(ONEt2) and Cp*Ti(Me)2(ONtBu(Me)) with B(C6F5)3 resulted in clean formation of the zwitterionic contact ion pairs [Cp*Ti(Me)(η2-ONEt2)]+[MeB(C6F5)3]− and [Cp*Ti(Me)(η2-ONtBu(Me))]+[MeB(C6F5)3]−, respectively

  类型的CP * TIX的络合物2（ONR'R''）（CP * =η 5 -C 5我5 ; X = Me中，氯; R = R'=的Et，TEMPO（2,2,6,6-四甲基哌啶-N-氧基）; X = R'= Me，R''= t Bu）是通过几种途径合成的。在用[Ph 3 C] + [B（C 6 F 5）4 ] -和Al i Bu 3活化后，这些配合物产生了用于丙烯聚合的高活性催化剂，尽管观察到明显的催化剂失活。用B（C 6 F 5）3 / Al活化我卜3或甲基铝氧烷（MAO）导致降低的聚合活性，后者导致增加的催化剂寿命。模型的研究表明，阿尔梅的相互作用3再用CP *的Ti（Me）的2（ONET 2）导致形成的CP *的Ti（Me）的2（η 2 -O（阿尔梅3）净2）。的X射线晶体结构证实，该配体hydroxylaminato保持η 2绑定到具有阿尔梅钛中心3通过hydroxylaminato配
• Half-Sandwich Group 4 Salicyloxazoline Catalysts
  作者：Stuart R. Coles、Guy J. Clarkson、Andrew L. Gott、Ian J. Munslow、Stefan K. Spitzmesser、Peter Scott

  DOI：10.1021/om060687h

  日期：2006.12.1

  leads to catalysts for alkene polymerization, the nature of which depends on the cocatalyst chosen. The anilinium salt smoothly produces a single chiral species, [Cp*ZrLMe][B(C6F5)4], detected also by 1H NMR spectroscopy, which is a highly active single-site catalyst for polymerization of ethene (and less active for copolymerization of ethene/hexene). The trityl activator produces the same catalyst and

  已经通过除盐和质子分解途径制备了带有Cp *和水杨基恶唑啉酮（L）配体的新型锆和ha半三明治复合物。相似的Cp和茚基化合物通常难以获得，钛化合物也是如此。根据变温NMR研究，四个实例[Cp * MLX 2 ]的分子结构（不同的M = Zr，Hf; X = Cl，Me）显示出在溶液中持续存在的手性金属结构。Δ ģ ⧧ 298用于外消旋化过程被发现是大约 75 kJ mol -1。用MAO，[Ph 3 C] [B（C 6 F 5）4 ]或[PhNMe 2 H] [B（C ）处理这些化合物6 F 5）4 ]导致用于烯烃聚合的催化剂，其性质取决于所选择的助催化剂。苯胺盐可平稳地产生单个手性物质[Cp * ZrLMe] [B（C 6 F 5）4 ]，也可通过1检测到1 H NMR光谱学，它是用于乙烯聚合的高活性单中心催化剂（而对于乙烯/己烯的共聚活性较低）。三苯甲基活化剂产生相同的催化剂和至少一种其
• Isospecific polymerization of 1-hexene by C₁-symmetric half-metallocene dimethyl complexes of group 4 metals with bidentate N-substituted iminomethylpyrrolyl ligands
  作者：Takahiro Yasumoto、Keishi Yamamoto、Hayato Tsurugi、Kazushi Mashima

  DOI：10.1039/c2dt32481d

  日期：——

  Non-bridged half-metallocene dimethyl complexes of group 4 metals 2a–4a with an N-4-methoxyphenyl(iminomethyl)pyrrolyl ligand 1a were synthesized and characterized by NMR spectroscopy and X-ray analysis. Upon activation with [Ph3C][B(C6F5)4], these complexes became active catalysts for the polymerization of 1-hexene. A series of hafnium complexes with various N-substituents on the imine group of ligands 1b–1g were also prepared and applied as catalysts for 1-hexene polymerization. The activation parameters for the exchange process between the two methyl groups bound to the metal for Cp*MMe2(R-pyr) complexes were estimated by NMR shape analysis at various temperatures. The findings indicated that the transition state of the ligand flipping process might be associated with the isoselectivity of the polymerization reaction.

  合成了第 4 族金属 2a-4a 与 N-4-甲氧基苯基（亚氨基甲基）吡咯配体 1a 的非杂化半茂金属二甲基配合物，并通过核磁共振光谱和 X 射线分析对其进行了表征。这些配合物在[Ph3C][B(C6F5)4]活化后，成为 1-己烯聚合的活性催化剂。此外，还制备了一系列配体 1b-1g 的亚胺基上含有不同 N 取代基的铪配合物，并将其用作 1-己烯聚合的催化剂。通过核磁共振形状分析，估算了 Cp*MMe2(R-pyr) 复合物在不同温度下与金属结合的两个甲基之间交换过程的活化参数。研究结果表明，配体翻转过程的过渡态可能与聚合反应的等选择性有关。
• Sterically Encumbered (Perfluoroaryl) Borane and Aluminate Cocatalysts for Tuning Cation−Anion Ion Pair Structure and Reactivity in Metallocene Polymerization Processes. A Synthetic, Structural, and Polymerization Study
  作者：You-Xian (Eugene) Chen、Matthew V. Metz、Liting Li、Charlotte L. Stern、Tobin J. Marks

  DOI：10.1021/ja973769t

  日期：1998.7.1

  The synthesis and dialkyl abstraction chemistry as well as the unusual cocatalytic characteristics in metallocene-mediated polymerization of two distinctive borane and aluminate cocatalysts tris(2,2',2"-nonafluorobiphenyl)borane (PBB) and triphenyl carbenium tris(2,2',2"-nonafluorobiphenyl)fluoroaluminate, (Ph(3)C(+)PBA(-)) are reported. Reaction of PBB with Cp'2ThMe2 (Cp' = eta(5)-C5Me5), CGCZrMe(2) (CGC = Me2-Si(eta(5)-Me4C5)('BuN)), and Cp'MMe3 (M = Zr, Hf) cleanly affords base-free cationic complexes Cp'2ThMe+MePBB- (1), CGCZrMe(+)MePBB(-) (5), and Cp'MMe2+MePBB- (M = Zr, 7; Hf, 8), in case of CGCTiMe(2) and dimethyl zirconocenes, mu-methyl dinuclear cationic complexes [(CGeTiMe)(2)(mu-Me)](+) MePBB- (6) and [(L2ZrMe)(2)(mu-Me)]+MePBB- (L = eta(5)-C5H5 (CP), 2; eta(5)-1,2-Me2C5H3 (CP''), 3; Cp', 4; L-2 = Me2Si(Ind)(2), Ind = eta(5)-C9H6, 9; L-2 = Me2C(Flu)(Cp), Flu = eta(5)-C13H8, 10) are formed. A similar reaction with Ph3C+PBA- results in the corresponding complexes CGCZrCH(3)(+)PBA(-) (M = Zr, 19; Ti, 20) and L(2)ZrCH(3)(+)PBA(-) (L = Cp, 15b; Cp", 16; eta(5)-1,3-(SiMe2)(2)C5H3, 17; Cp', 18; L-2 = Me2Si(Ind)(2), 21; L-2 = Me2C(Flu)(Cp), 22). Two dinuclear complexes 3 and 13 ([Me2C(Flu)(Cp)Zr(C6F5)](2)(mu-F)+MeB(C6F5)(3)(-)) derived from borane PBB and B(C6F5)(3), respectively, and three other PBA(-)-based monomeric complexes 14 (Ph(3)C(+)PBA(-)), 19, and 21 have been characterized by X-ray diffraction, and these determinations allow detailed analysis of the ion pairing in the solid state. In combination with solution dynamic NMR, all data indicate MePBB--cation interactions to be considerably weaker than those involving MeB(C6F5)(3)(-), while the strongly ion-paired chiral PBA(-) converts previously enantiomeric cations into pairs of diastereomers. As revealed by dynamic H-1 NMR studies, ion pair reorganization/symmetrization in 5 is significantly more rapid than in the MeB(C6F5)(3)(-) analogue, suggesting much looser ion pairing in 5. On the other hand, PBA- racemization is a rapid process (e.g., Delta G double dagger(58 degrees C) = 16.9(2) kcal/mol for 16), while cation-PBA(-) ion pairs have higher barriers for ion pair symmetrization than in analogous fluoroaryl borates. Dinuclear complexes 2 and 3 initiate efficient polymerization of methyl methacrylate (MMA) to produce syndiotactic poly(methyl methacrylate) (PMMA), while 9 produces highly isotactic PMMA, and sterically more accessible complexes 6 and 10 exhibit no activity.For olefin polymerization and copolymerization, PBB-derived cationic complexes, both monomeric and dinuclear, generally exhibit higher catalytic activity and comonomer incorporation levels than the MeB(C6F5)(3)(-) analogues, with CGC catalysts exhibiting the greatest activity contrasts. On the other hand, PBA(-)-derived complexes exhibit a remarkable sensitivity of olefin polymerization characteristics and ion pairing to ancillary ligand bulk, with activity differences of up to 10(6)-fold observed. Ln regard to stereospecific polymerization, PBA--derived chiral complex 21 produces highly isotactic polypropylene while B(C6F5)(4)(-)- derived analogue produces isotactic polypropylene with lower isotacticity under similar conditions. Microstructure analyses of poly(ethylene-co-1-hexene) samples indicate that PBB enhances comonomer incorporation randomness.
• 2,4,6-Trimethylpyridine–bishydrofluoride: a novel fluorinating reagent for organo transition-metal alkyls
  作者：Axel Herzog、Herbert W. Roesky、Felix Jäger、Alexander Steiner

  DOI：10.1039/cc9960000029

  日期：——

  Complexes [M(eta(5)-C(5)Me(5))F-3] (M = Zr 2, Hf 5), [Zr(eta(5)-C5H5)F-2] 7 and [Hf(eta(5)-C(5)Me(5))(2)F-2] 8 are obtained by treating the corresponding metal alkyls with [tmpy .(HF)(2)] (tmpy = 2,4,6-trimethylpyridine); using an excess of [tmpy .(HF)(2)] in the preparation of 2 and 5 leads to the complexes [Htmpy][M(eta(5)-C(5)Me(5))F-2}(mu-F)(3)] (M = Zr 3, Hf 6), respectively and a crystal structure determination of 3 confirms its ionic nature; [Ti(eta(5)-C(5)Me(5))Cl2F] 10 and 2 were synthesised also from their corresponding alkyls by alkyl-fluorine exchange using Me(3)SnF.