Cp*2TiF2 | 87050-22-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: Cp*2TiF2
• 英文别名: Cp*₂TiF₂
• CAS: 87050-22-4
• 化学式: C₂₀H₃₀F₂Ti
• 分子量: 356.335
• InChiKey: AIEAPZHTWVIYRQ-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：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Cp*2TiF2 、 二异丁基氢化铝 以 四氢呋喃 、 环己烷 为溶剂， 以23%的产率得到Cp*2Ti(μ-H)2AliBu2
  参考文献：
  名称：

  Group 4 metallocene catalysed full dehydrogenation of hydrazine borane

  摘要：

  肼硼烷 (H2N–NH2·BH3) 完全脱氢生成气态产物 H2 和 N2 的研究，由多种类型为 Cp′2M(L)(η2-Me3SiC2SiMe3) (Cp) 的 4 族茂金属炔配合物催化' = 取代或未取代的 η5-环戊二烯基；M = Ti，无 L；M = Zr，L = 吡啶）和第 4 族金属茂氢化物。体积数据表明，释放的氢量强烈依赖于金属和环戊二烯基配体。

  DOI：

  10.1039/c3dt51370j
• 作为产物：
  描述：

  [(pentanethylcyclopentadienyl)2Ti(η1-fluorobenzene)][B(pehenyl)4] 在 α,α,α-trifluorotoluene 作用下， 以 氟苯 为溶剂， 生成 Cp*2TiF2
  参考文献：
  名称：

  十甲基二茂钛阳离子的结构，具有两个 Agostic C−H 键的茂金属及其与碳氟化合物的相互作用†

  摘要：

  十甲基二茂钛阳离子的四苯基硼酸盐 [Cp*2Ti][BPh4] (1, Cp* = C5Me5) 是通过 Cp*2TiH 与 [Cp2Fe][BPh4] 的反应以及 Cp*2TiMe 与 [ PhNMe2H][BPh4]。1 的晶体结构表明，Cp*2Ti 阳离子具有弯曲的茂金属结构，与 Cp* 配体之一上的两个相邻甲基的金属中心具有积极的相互作用。化合物 1 很容易与 THF 反应生成加合物 [Cp*2Ti(THF)][BPh4] (2)。在氟苯中，1 形成 eta1-氟苯加合物 [Cp*2Ti(eta1-FC6H5)][BPh4] (3)，并对其进行了结构表征。与 3 的热稳定性相反，将 α,α,α-三氟甲苯添加到 1 或 2 会导致 CF 活化，得到 Cp*2TiF2 和 PhCF2CF2Ph 作为主要产物。

  DOI：

  10.1021/ja027617w

文献信息

• Selective C–H and C–F Bond Activation Reactions of Pyridine and Fluoropyridines – Formation of Binuclear μ‐X Titanocene Complexes (X = H, F) with α‐Functionalized N‐Heterocycles
  作者：Ingmar M. Piglosiewicz、Susanne Kraft、Rüdiger Beckhaus、Detlev Haase、Wolfgang Saak

  DOI：10.1002/ejic.200400252

  日期：2005.3

  Titanocene synthons react with pyridine (2), fluorosubstituted pyridines [pentafluoropyridine (3), 2-fluoropyridine(4)] and cyanuric fluoride, by C–H and C–F bond activation, respectively, to afford interesting novel binuclear titanium(III) complexes. C–H bond activation requires high temperatures (110 °C), whereas C–F bond activation occurs at room temperature. X-ray structure analysis showed that

  茂钛合成子分别与吡啶 (2)、氟取代的吡啶 [五氟吡啶 (3)、2-氟吡啶 (4)] 和氰尿酰氟反应，分别通过 C-H 和 C-F 键活化，得到有趣的新型双核钛 (III)复合体。C-H 键活化需要高温 (110 °C)，而 C-F 键活化发生在室温下。X 射线结构分析表明，当吡啶与二茂钛片段反应时，两个钛 (III) 中心是氢化桥联的，如果使用吡啶的 2-氟取代衍生物，则是氟桥联。在使用 2-氟吡啶的竞争实验中比较了 2 位 C-F 和 C-H 键对二茂钛片段的反应性——揭示了对 C-F 键裂解的偏好。使用 [Cp*2Tiη2-C2(SiMe3)2}] 代替非甲基化二茂钛源，已通过 NMR 测量在溶液中证明了初级单核 C-F 键活化产物。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Difference in Reactivity of Cyclopentadienyltitanium Fluorides and Chlorides Using AlR₃ (R = Me, Et):  Syntheses and Structures of Ti(III)−F(Cl)−Al Compounds (η⁵-C₅Me₅)₂Ti₂(μ-Cl)₆Al₂Me₄, (η⁵-C₅Me₅)₂Ti₂(μ-F)₈Al₄Me₈, and [(η⁵-C₅H₄Me)₂Ti(μ-F)₂AlEt₂]₂
  作者：Peihua Yu、Peter Müller、Musa A. Said、Herbert W. Roesky、Isabel Usón、Guangcai Bai、Mathias Noltemeyer

  DOI：10.1021/om9809163

  日期：1999.4.1

  (Cp*TiF2Me)(AlMe2F) (2b), respectively, whereas under thermal conditions the reduced titanium species Cp*2Ti2(μ-Cl)6Al2Me4 (3) and Cp*2Ti2(μ-F)8Al4Me8 (4) were obtained in moderate yields. The reduction of Ti(IV) to Ti(III) is observed when Cp‘2TiF2 (Cp‘ = η5-C5H5, η5-C5H4Me, Cp*) and Cp*TiF3 are treated with AlEt3, leading to [Cp‘2Ti(μ-F)2AlEt2]2 [Cp‘ = η5-C5H5 (5), η5-C5H4Me (6), Cp* (7)] and Cp*2Ti2(μ-F)8Al4Et8

  的Cp * TIX的反应3 [X = Cl（上1A），F（图1b）中，Cp * =η 5 -C 5我5 ]用过量的阿尔梅3得到甲基化产物的Cp *的TiCl 2我（图2a）和（Cp * TiF 2 Me）（AlMe 2 F）（2b），而在热条件下，还原的钛物种Cp * 2 Ti 2（μ-Cl）6 Al 2 Me 4（3）和Cp * 2 Ti 2（μF）8铝4Me 8（4）以中等产率获得。当CP '的Ti（IV）与Ti（III）的还原，观察到2的TiF 2（CP'=η 5 -C 5 H ^ 5，η 5 -C 5 H ^ 4 Me中的Cp *）1和Cp *的TiF 3是与ALET处理3，从而导致[CP ' 2的Ti（μ-F）2 ALET 2 ] 2 [CP'=η 5 -C 5 H ^ 5（5），η 5 -C 5 H ^ 4我（6），Cp *（7）]和Cp * 2 Ti 2（μ-F）8 Al 4
• Synthesis and spectroscopic characterization of a series of substituted cyclopentadienyl Group 4 fluorides; crystal structure of the acetylacetonato complex [(acac)₂(η-C₅Me₅)Zr(µ-F)SnMe₃Cl]
  作者：Eamonn F. Murphy、Peihua Yu、Stefan Dietrich、Herbert W. Roesky、Emilio Parisini、Mathias Noltemeyer

  DOI：10.1039/dt9960001983

  日期：——

  A series of mono- and di-substituted cyclopentadienyl Group 4 fluorides [Tiη-C5H3R(R′)-1,3}nFm], (n=m= 2 and n= 1, m= 3; R = H or SiMe3; R′= H, Me or SiMe3), [Ti(η-C5Me5)2F2] and [Zr(η-C5H5)2F2] have been prepared via the reaction of the corresponding chlorides with SnMe3F. The compounds have been characterized by means of 1H and 19F NMR, IR and mass spectroscopy and chemical analyses. The solvent

  一系列单和二取代的环戊二烯第4族氟化物钛[Ti η-C 5 H ^ 3 R（R'） - 1,3} Ñ ˚F米]，（Ñ =米= 2和Ñ = 1，米= 3; R = H或森达3 ; R'= H，Me或森达3），钛[Ti（η-C 5我5）2 ˚F 2 ]和[Zr的（η-C 5 H ^ 5）2 ˚F 2 ]有制备通过与SnMe相应的氯化物的反应3 F.化合物已被表征借助于1 H和19 F NMR，IR和质谱以及化学分析。讨论了使用SnMe 3 F的反应的溶剂依赖性。为了证明这一点氟化系统的广泛的适用性的acetylacetonatofluoro配合物[（ACAC） 2（η-C 5我5基）Zr（μ-F）SnMe 3 CL]已经制备和它的晶体结构来确定。
• The Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors
  作者：Dan A. Smith、Torsten Beweries、Clemens Blasius、Naseralla Jasim、Ruqia Nazir、Sadia Nazir、Craig C. Robertson、Adrian C. Whitwood、Christopher A. Hunter、Lee Brammer、Robin N. Perutz

  DOI：10.1021/jacs.5b07509

  日期：2015.9.16

  The association constants and enthalpies for the binding of hydrogen bond donors to group 10 transition metal complexes featuring a single fluoride ligand (trans-[Ni(F)(2-C5NF4)(PR3)(2)], R = Et la, Cy lb, trans-[Pd(F) (4-C5NF4) (PCy3)(2)](2), trans-[Pt(F)2-C5NF2H(CF3)}-(PCy3)(2)] 3 and of group 4 difluorides (Cp2MF2, M = Ti 4a, Zr 5a, Hf 6a; Cp*2MF2, M = Ti 4b, Zr 5b, Hf 6b) are reported. These measurements allow placement of these fluoride ligands on the scales of organic H-bond acceptor strength. The H-bond acceptor capability beta (Hunter scale) for the group 10 metal fluorides is far greater (la 12.1, lb 9.7, 2 11.6, 3 11.0) than that for group 4 metal fluorides (4a 5.8, Sa 4.7, 6a 4.7, 4b 6.9, Sb 5.6, 6b 5.4), demonstrating that the group 10 fluorides are comparable to the strongest organic H-bond acceptors, such as Me3NO, whereas group 4 fluorides fall in the same range as N-bases aniline through pyridine. Additionally, the measurement of the binding enthalpy of 4-fluorophenol to la in carbon tetrachloride (-23.5 +/- 0.3 kJ mol(-1)) interlocks our study with Laurence's scale of H-bond basicity of organic molecules. The much greater polarity of group 10 metal fluorides than that of the group 4 metal fluorides is consistent with the importance of p pi-d pi- bonding in the latter. The polarity of the group 10 metal fluorides indicates their potential as building blocks for hydrogen-bonded assemblies. The synthesis of trans-[Ni(F)2-C5NF3(NH2)}(PEt3)(2)], which exhibits an extended chain structure assembled by hydrogen bonds between the amine and metal-fluoride groups, confirms this hypothesis.
• A π-Donor Spectrochemical Series for X in (Me₅C₅)₂TiX, and β-Agostic Interactions in X = Et and N(Me)Ph
  作者：Wayne W. Lukens、Milton R. Smith、Richard A. Andersen

  DOI：10.1021/ja953272o

  日期：1996.1.1

  The EPR and electronic spectra of d(1)-bent metallocene compounds of the type Cp*(2)TiX, where X is halide, alkoxide, amide, alkyl, or hydride and Cp* = Me(5)C(5), have been studied. Several of these compounds are new, and those with X = N(Me)H and F were characterized by X-ray crystallography. The crystal structure of Cp*2TiN(Me)H showed that the N(Me)H ligand lies on the plane defined by Cp*(centroid)-Ti-Cp*(centroid). This is the sterically most unfavorable conformation but allows maximum Ti-N pi-bonding. The anisotropic frozen solution EPR spectra were analyzed by the method used by Petersen and Dahl for the d(1)-metallocenes, Cp(2)VX(2), which gives g(x), g(y), and g(z). Although the values of g(x) and g(z) are relatively constant throughout the series, the value of g(y) varies with the pi-donor ability of X. The pi-donor series is N(Me)H approximate to NH2 approximate to OMe > OPh approximate to F > N(Me)Ph Cl > Br > I > H. Among the known alkyls, the pi-donor ability was Et > Me > n-Pr approximate to CH(2)CMe(3) > CH2C6H5, which is rationalized, in part, by a beta-agostic interaction in the case of Et. The beta-agostic interaction in Cp*(2)TiEt and in Cp*2TiN(Me)Ph was investigated by variable-temperature EPR spectroscopy giving an enthalpy and entropy for the agostic interaction. For Cp*(2)TiEt the parameters for the agostic interaction are Delta H degrees = -1.93(3) kcal/mol and Delta S degrees = -6.3(2) eu, and for Cp*2TiN(Me)Ph, Delta H degrees = -1.5(1) kcal/mol and Delta S degrees = -7.9(5) eu.