bis(η-methylcyclopentadienyl)difluorotitanium

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: bis(η-methylcyclopentadienyl)difluorotitanium
• 英文别名: (η(5)-C5H4Me)2TiF2；(η5-C5H4Me)2TiF2
• 化学式: C₁₂H₁₄F₂Ti
• 分子量: 244.12
• InChiKey: IXGRAULZMZRKSY-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.66
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis(η-methylcyclopentadienyl)difluorotitanium 在 Na#Hg 作用下， 以 甲苯 为溶剂， 以92%的产率得到
  参考文献：
  名称：

  氟化三甲基锡：一种用于制备有机金属氟化物的新型氟化试剂。

  摘要：

  Me3SnF (1) reacts with Cp'MCl3 to give Cp'MF3 (2, Cp' = C5Me5, M = Ti; 2a, Cp' = C5Me4Et, M = Ti; 2b, Cp' = C5H5, M = Ti; 2c, Cp' = C5H4Me5, M = Ti; 3, Cp' = C5Me5, M = Zr; 4, Cp' = C5Me5, M = Hf) in high yields. The reaction of Cp2TiCl2, [C5H3(Me)(SiMe3)]2ZrCl2, and (C5Me5)2HfCl2 with Me3SnF yields Cp2TiF2 (5), [C5H3(Me) (SiMe3)]2ZrF2 (6), and (CsMe5)2HfF2 (7), respectively. Treatment of (Cp*TiClO)3 (Cp* = C5Me5) with Me3SnF leads to the eight-membered ring (Cp*TiFO)4 (8). The reaction of the organotitanium(III) chlorides (Cp2TiCl)2 (Cp = C5H5), [(C5H4Me)2TiCl]2, and Cp*2TiCl with Me3SnF gives the corresponding fluorides (Cp2TiF)2 (9), [(C5H4Me)2TiF]2 (10), and Cp2*TiF (11), respectively. An alternative method for the preparation of compounds 9 and 10 is the reduction of Cp2TiF2 and (C5H4Me)2TiF2, respectively, using sodium amalgam. The structures of 2c, 3, 4, and 10 were determined by single-crystal X-ray diffraction. Compounds 3 and 4 are isostructural and form tetramers in the solid as well as in solution. 10 is a fluorine-bridged dimer in the crystalline state.

  DOI：

  10.1021/om00016a030
• 作为产物：
  描述：

  二(甲基环戊二烯基)二氯化钛 、 三甲基氟锡烷 以 甲苯 为溶剂， 以90%的产率得到bis(η-methylcyclopentadienyl)difluorotitanium
  参考文献：
  名称：

  一系列取代的环戊二烯基第4族氟化物的合成和光谱表征；的晶体结构的乙酰丙酮络合物[（ACAC）2（η-C 5我5基）Zr（μ-F）SnMe 3 CL]

  摘要：

  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。

  DOI：

  10.1039/dt9960001983

文献信息

• 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。
• Syntheses and Properties of Cyclopentadienyl-Substituted Imidotitanium Fluorides
  作者：Feng-Quan Liu、Axel Herzog、Herbert W. Roesky、Isabel Usón

  DOI：10.1021/ic950778z

  日期：1996.1.1

  The reaction of 2 equiv of Me(3)SnF with [(eta(5)-C(5)H(4)Me)TiCl(NPh)](2) in the presence of at least 2 equiv of pyridine affords [(eta(5)-C(5)H(4)Me)TiF(NPh)](2) (1) in high yield. (eta(5)-C(5)H(4)SiMe(3))TiCl(N-t-Bu). py reacts quantitatively with an equimolar amount of Me(3)SnF to yield [(eta(5)-C(5)H(4)SiMe(3))TiF(N-t-Bu)](2) (2). The fluorides [eta(5)-Cp'TiF(NSnMe(3))](2) (Cp' = C(5)Me(4)Et (3), C(5)H(4)Me (4)) are obtained in high yield by reaction of N(SnMe(3))(3) with (eta(5)-C(5)Me(4)Et)TiF3 and (eta(5)-C(5)H(4)Me)TiF3, respectively. Complex 3 has been characterized by X-ray diffraction. (MeAlNMes)(4)(Mes = 2,4,6-trimethylphenyl) reacts as a transamination reagent with 4 equiv of (eta(5)-C(5)H(4)Me)(2)TiF2 to provide [(eta(5)-C(5)H(4)Me)TiF(NMes)](2) (5) in low yield.
• Isolation and characterization of bis(η-methylcyclopntadienyl)dihalotitanium(IV)
  作者：Kailash Chandra、R.K. Sharma、B.S. Garg、R.P. Singh

  DOI：10.1016/s0020-1693(00)95529-4

  日期：1979.1
• Liu, Feng-quan; Gornitzka, Heinz; Stalke, Dietmar, Angewandte Chemie, <hi>1993</hi>, vol. 105, p. 447 - 448
  作者：Liu, Feng-quan、Gornitzka, Heinz、Stalke, Dietmar、Roesky, Herbert W.

  DOI：——

  日期：——