(η5-C5H5)(η5-C5H4(CH2)2P(phenyl)2)TiCl2 | 83311-42-6

• 英文名称: (η5-C5H5)(η5-C5H4(CH2)2P(phenyl)2)TiCl2
• 英文别名: [(η5-C5H5)(η5-C5H4(CH2)2P(C6H5)2)TiCl2]；[TiCl2(η5-C5H5)(η5-C5H4(CH2)2P(C6H5)2)]；[(η5-C5H5)TiCl2(η5-C5H4(CH2)2PPh2)]
• CAS: 83311-42-6
• 化学式: C₂₄H₂₃Cl₂PTi
• 分子量: 461.206
• InChiKey: YUNGSSIYUHAKBI-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：
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• 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-C5H5)(η5-C5H4(CH2)2P(phenyl)2)TiCl2 在 氢化铝 作用下， 以 not given 为溶剂， 生成 [(η5-C5H5)(η5:η1-C5H4(CH2)2P(C6H5)2)TiCl]
  参考文献：
  名称：

  钛烷和锆的配位体环戊二烯基二苯基膦和环戊二烯基乙基二苯基膦的配合物：结构异双金属

  摘要：

  的Ph反应2 P（CH 2）Ñ（C 5 H ^ 4）锂，（Ñ = 0，2），具有的MC1 4或CpTiCl 3（M =钛，锆; CP =η 5 -C 5 H ^ 5）形式CL 2 M [（η 5 -C 5 H ^ 4）（CH 2）ñ PPH 2 ] 2或Cl 2的CpTI [（η 5 -C 5 H ^ 4） - （CH 2）2 PPH 2]，产量高。描述了在CO下用Al进行化学还原或这些配合物的电化学还原。钛（IV）和锆（IV）衍生物与羰基金属（Mo（CO）6，Cr（CO）6，Fe（CO）5，Mo（CO）4（C 8 H 12））反应形成新的杂双金属配合物。减少了Cl的铝2的CpTI [（η 5 -C 5 H ^ 4）（CH 2）2 PPH 2 ]的Mo（CO）5下CO结果在含有低化合价钛的新的异种。两个络合物Cl 2 M [（η5 -C 5 H 4）（CH 2）2 PPh 2 ] 2（M =

  DOI：

  10.1016/s0022-328x(00)92897-3
• 作为产物：
  描述：

  三氯一茂钛 、 lithium{2-(diphenylphosphanyl)ethyl}cyclopentadienide 以 四氢呋喃 为溶剂， 以85%的产率得到(η5-C5H5)(η5-C5H4(CH2)2P(phenyl)2)TiCl2
  参考文献：
  名称：

  Synthesis and structural studies of TiRu polymetallic systems

  摘要：

  The reaction of the titanocene monophosphines 1 and 2 with the dimer [(p-cymene)RuCl2](2) give the heterobimetallic compounds (p-cymene)[(eta(5)-C5H4)(mu-eta(5):eta(1)-C5H4PPh2)TiCl2]RuCl2 and (p-cymene)[(eta(5)-C5H4)(mu-eta(5):eta(1)-C5H4CH2CH2PPh2)TiCl2]RuCl2, respectively. Both structures have been confirmed by X-ray diffraction. By using same procedure, the synthesis of a trimetallic complex Ru-Ti-Ru has been achieved. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00219-9

文献信息

• Towards a Library of “Early‐Late” Ti–Ru Bimetallic Complexes
  作者：Laurianne Bareille、Pierre Le Gendre、Philippe Richard、Claude Moïse

  DOI：10.1002/ejic.200401028

  日期：2005.6

  titanium atom of the complexes [TiCl2(η5-C5H5)η5-C5H4(CH2)2PR2}] (1: R = Ph; 2: R = Cy) by sodium fluoride or sodium benzoate in two-phase systems. Treatment of these new metalloligands with the binuclear complex [(p-cymene)RuCl2]2 affords the targeted titanocene difluoride and titanocene dibenzoate bimetallic ruthenium complexes 8–11. The first chiral Ti–Ru bimetallic complex 12 bearing a binaphthyloxy

  通过替换配合物 [TiCl2(η5-C5H5)η5-C5H4(CH2)2PR2}] (1: R = Ph; 2: R = Cy) 由氟化钠或苯甲酸钠在两相系统中得到。用双核配合物 [(p-cymene)RuCl2]2 处理这些新的金属配体，得到目标二氟化钛和二茂钛二苯甲酸二金属钌配合物 8-11。以这种方式合成了第一个在钛中心带有联萘氧基配体的手性 Ti-Ru 双金属配合物 12。在每个系列中，已经确定了 X 射线晶体结构。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• The Taming of Redox‐Labile Phosphidotitanocene Cations
  作者：Adrien T. Normand、Quentin Bonnin、Stéphane Brandès、Philippe Richard、Paul Fleurat‐Lessard、Charles H. Devillers、Cédric Balan、Pierre Le Gendre、Gerald Kehr、Gerhard Erker

  DOI：10.1002/chem.201805430

  日期：2019.2.21

  spectroscopy, X‐ray diffraction analysis) and through DFT calculations. The theoretical analysis of the bonding situation by using the electron localization function (ELF) shows the presence of π‐interactions between the phosphido ligand and Ti in the d0 complexes, whereas dπ–pπ repulsion prevents such interactions in the d1 complexes. In addition, CH–π interactions were observed in several complexes, both

  报道了用叔膦环侧链稳定的d e 0磷杂环丁烷阳离子。这些化合物是通过用[Cp 2 Fe] [BPh 4 ]对d 1前体进行单电子氧化而获得的。通过实验（EPR，UV / Vis和NMR光谱，X射线衍射分析）并通过DFT计算研究了这些化合物的电子结构。通过使用电子本地化功能（ELF）对键合情况的理论分析表明，在d 0配合物中磷配体与Ti之间存在π相互作用，而dπ–pπ排斥阻止了d 1中的这种相互作用。复合体。此外，在磷配体和膦环之间的溶液和固体中的几种配合物中都观察到CH-π相互作用。发现d 0配合物对光敏感，并通过Ti-P键均质分解而得到Ti III物种。通过与二苯乙炔反应捕获了裸露的d 0磷钛杂环丁烯阳离子，生成了Ti / P阻抑的路易斯对（FLP），发现该反应对的活性比以前报道的Zr类似物低。
• Evidence of intramolecular electron transfer between two metallic atoms in a bimetallic complex by electrochemical methods
  作者：Hélène Cattey、Alain Vallat、Pierre Le Gendre、David Evrard、Claude Moïse、Yves Mugnier

  DOI：10.1039/b507665j

  日期：——

  [(η5-C5H5)(μ-η5:η1-C5H4(CH2)2P(C6H5)2TiCl2] 1 and the heterobimetallic complex [(η5-C5H5)(μ-η5:η1-C5H4(CH2)2P(C6H5)2TiCl2][RuCl2(C6H4(CH3)(C3H7))] 2 have been studied by cyclic voltammetry, controlled potential electrolysis and rotating disk electrode voltammetry. An unexpected electron transfer between the two heterobimetallic atoms has been observed. This transfer takes place via an intramolecular interaction

  [（η单体复合物的电化学性能5 -C 5 H ^ 5）（μ-η 5：η 1 -C 5 ħ 4（CH 2）2 P（C 6 H ^ 5）2的TiCl 2 ] 1和的异配合物[（η 5 -C 5 H ^ 5）（μ-η 5：η 1 -C 5 ħ 4（CH 2）2 P（C 6 H ^ 5）2通过以下方法研究了TiCl 2 ] [RuCl 2（C 6 H 4（CH 3）（C 3 H 7））] 2。循环伏安法，可控电位电解和转盘电极 伏安法。意外电子转移已经观察到两个杂双金属原子之间。该转移通过分子内相互作用发生，因此通过氯离子桥发生。进行了电化学模拟，以验证实验结果并获得所提出的方方案的动力学常数。
• Synthesis of enol esters catalysed by 'early–late' Ti–Ru complexes
  作者：P Le Gendre

  DOI：10.1016/s0020-1693(02)01563-3

  日期：2003.7.4

  The titane-ruthenium heterobimetallic compounds (p-cymene)[(eta(5)-C5H5)(mu-eta(5):eta(1)-C5H4(CH2)(m)PR2)TiCl2]RuCl2 4-6 have been revealed to be quite good catalysts for the addition of formic acid to 1-hexyne and phenylacetylene. These preliminary results led us to synthesize new tetrametallic complexes 10-12 via the reaction of the titanocene phosphanes 1-3 with the polymer [Ru(CO)(2)(mu-O2CH)](n). Their catalytic ability for the enol esters formation has been studied. (C) 2003 Elsevier Science B.V. All rights reserved.
• Multinuclear Cytotoxic Metallodrugs: Physicochemical Characterization and Biological Properties of Novel Heteronuclear Gold–Titanium Complexes
  作者：Margot Wenzel、Benoît Bertrand、Marie-Joëlle Eymin、Virginie Comte、Jennifer A. Harvey、Philippe Richard、Michael Groessl、Olivier Zava、Hedi Amrouche、Pierre D. Harvey、Pierre Le Gendre、Michel Picquet、Angela Casini

  DOI：10.1021/ic201155y

  日期：2011.10.3

  An unprecedented series of titanocene-gold bi- and trimetallic complexes of the general formula [[(eta(5)-C5H5)-(mu-eta(5):kappa(1)-C5H4(CH2)(n)PPh2)TiCl2](m)AuClx](q+) (n = 0, 2, or 4; m = 1, x =1, q = 0 or m = 2, x = 0, q = 1) have been prepared and characterized spectroscopically. The luminescence spectroscopy and photophysics of one of the compounds, [[(eta(5)-C5H5)-(mu-eta(5):kappa(1)-C5H4PPh2)TiCl2](2)Au]PF6, have been investigated in 2MeTHF solution and in the solid state at 77 and 298 K. Evidence for interfragment interactions based on the comparison of electronic band positions and emission lifetimes, namely, triplet energy transfer (ET) from the Au- to the Ti-containing chromophores, is provided. The cytotoxicity of the complexes was evaluated on A2780 ovarian cancer cells and on their cisplatin-resistant cell line A2780cisR; the compounds showed activity in the low micromolar range that was markedly more active than the corresponding titanocene-phosphine precursors [(eta 5-C5H5)(eta(5)-C5H4(CH2)(n)PPh2)TiCl2], cisplatin, and, for some of them, the gold analogue [(PPh3)AuCl]. In an attempt to draw preliminary structure activity relationships, cell uptake measurements and interaction studies with plasmid DNA and the model protein ubiquitin (Ub) have been undertaken on some of the compounds.