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
• New Fluoride Derivative of a Dinuclear Titanium(III) Fulvalene Complex:  Crystal Structure of [(η⁵-C₅H₅)Ti(μ-F)]₂(μ-η⁵:η⁵-C₁₀H₈)
  作者：Peihua Yu、Eamonn F. Murphy、Herbert W. Roesky、Paolo Lubini、Hans-Georg Schmidt、Mathias Noltemeyer

  DOI：10.1021/om9606808

  日期：1997.2.1

  Reduction of titanocene difluoride (Cp(2)TiF(2)) with 1.5 equiv of potassium in toluene at 60-100 degrees C affords the dinuclear eta(5):eta(5)-fulvalene complex [(eta(5)-C5H5)Ti(mu-F)](2)(mu-eta(5):eta(5)-C10H8) (2). 2 was also obtained via reaction of Me(3)SnF with the corresponding chloride and hydride compounds [(eta(5)-C5H5)Ti(mu-X)](2)(mu-eta(5):eta 5-C10H8) (X = Cl, H), 2 has been characterized by mass spectrometry, IR spectroscopy, and chemical analyses. The molecular structure of 2, as determined by the X-ray crystal structural analyses, reveals a Ti2F2 fragment symmetrically folded along the Ti-Ti direction and assuming a butterfly configuration with a dihedral angle of 27.6(2)degrees. A dihedral angle of 15.3(3)degrees is observed between the two C5H4 rings of the folded fulvalene ligand.
• 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：——