Ti[N(Bu(t))Ph]3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Ti[N(Bu(t))Ph]3
• 英文别名: Ti(N[t-Bu]Ph)3；Tert-butyl(phenyl)azanide;titanium(3+)
• 化学式: C₃₀H₄₂N₃Ti
• 分子量: 492.564
• InChiKey: YNBXEQXVANJQGB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.47
• 重原子数：
  34
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Ti[N(Bu(t))Ph]3 、 二氧化碳 以 乙醚 为溶剂， 生成 Ti2[μ-O2CN(Bu(t))Ph]4(N(Bu(t))Ph)2
  参考文献：
  名称：

  A Diamagnetic Dititanium(III) Paddlewheel Complex with No Direct Metal−Metal Bond

  摘要：

  Reaction of Ti[N(Bu-t) Ar](3) (Ar = 3,5-C6H3Me2 or Ar' = C6H5) with CO2 at - 40 degrees C produces diamagmetic Ti-III paddlewheel complexes with long Ti - Ti separations (> 3.4 angstrom), thus excluding direct Ti - Ti bonding. H-1 NMR spectroscopy shows that the compounds are diamagnetic in solution in the temperature range of - 65 to + 70 degrees C. In the solid state, the diamagnetism was found to persist between 2 and 300 K. Calculations at the density functional theory level suggest that the diamagnetism results from antiferromagnetic coupling by superexchange through the ligand pi system.

  DOI：

  10.1021/ic0602650
• 作为产物：
  描述：

  四氢呋喃氯化钛 、 在 (CH₃)2NCH₂CH₂N(CH₃)2 作用下， 以 乙醚 为溶剂， 以75%的产率得到Ti[N(Bu(t))Ph]3
  参考文献：
  名称：

  通过自由基醇盐 C-O 裂解组装钼/钛 μ-氧配合物

  摘要：

  三配位 Ti(NRAr)3 [R = C(CD3)2(CH3), Ar = C6H3Me2] 通过钠汞齐还原 ClTi(NRAr)3 以 73% 的产率制备，在 TiCl3( THF)3 与 3 当量的 Li(NRAr)(OEt2) 在 TMEDA 存在下。在 TMEDA 存在下，通过用 3 当量的 Li(tBuNPh)(OEt2) 处理 TiCl3(THF)3，类似地制备了 Ti(tBuNPh)3，产率为 75%。Ti(NRAr)3 与 NMo(OtBu)3 在烃溶剂中在 -35 °C 下反应生成一种热不稳定的中间体，公式为 (tBuO)3Mo[μ-N]Ti(NRAr)3，它很容易失去叔丁基自由基并在 25 °C 下异构化。后一个过程的动力学是在 20-60 °C 的温度范围内获得的；该过程表现出干净的一阶行为。获得以下活化参数：ΔH⧧ = 21.4 ± 0.2 kcal mol-1 和

  DOI：

  10.1021/ja960564w

文献信息

• Heterobimetallic Reductive Cross-Coupling of Benzonitrile with Carbon Dioxide, Pyridine, and Benzophenone
  作者：Arjun Mendiratta、Christopher C. Cummins

  DOI：10.1021/ic051320s

  日期：2005.10.1

  6-Me2C6H3CN. In the case of the couplings involving pyridine and benzophenone, C-C bond formation takes place with dearomatization, with the new C-C bond being formed between the nitrile carbon of PhCN and the para carbon of pyridine or one of the benzophenone phenyl groups. Of the radical metal complex/substrate adducts invoked in this work, that between titanium(III) and CO2 is the only one not directly observable

  本文描述的是钼（III）配合物Mo（N [t-Bu] Ar）3（Ar = 3,5-C6H3Me2）和钛（III）配合物与二氧化碳之间的杂双金属自由基交叉偶联反应，吡啶和二苯甲酮。所使用的钛（III）系统是Ti（N [t-Bu] Ar）3（Ar ＝ 3，5-C 6 H 3 Me 2）或Ti（N [t-Bu] Ph）3。描述了Mo / PhCN / CO2 / Ti耦合系统的晶体结构研究，以及Mo / PhCN / Ph2CO / Ti耦合系统的类似物，其中PhCN被2,6-Me2C6H3CN取代。在涉及吡啶和二苯甲酮的偶联的情况下，CC键的形成伴随脱芳香化作用而发生，其中新的CC键在PhCN的腈碳与吡啶的对碳或二苯甲酮苯基之一之间形成。在这项工作中引用的自由基金属络合物/底物加合物中，钛（III）和二氧化碳之间的关系是唯一不能直接观察到的。在所有情况下，选择性交叉偶联反应均解释为钛（III）底物配合物（底物=
• Synthesis of mer-trichlorotris(tetrahydrofuran) tungsten(III) by intermetal chlorine atom transfer
  作者：Esther Kim、Aaron L. Odom、Christopher C. Cummins

  DOI：10.1016/s0020-1693(97)06157-4

  日期：1998.8

  The three-coordinate titanium(III) complex Ti(N[R]Ar)(3) (R = C(CD3)(2)CH3, Ar = 3,5-C6H3Me2) abstracts chlorine from WCl4 ( DME) (DME = 1,2-dimethoxyethane) in tetrahydrofuran (THF) to give yellow crystalline WCl3 (THF)(3) in 65% isolated yield. Orange TiCl(N[R]Ar)(3), which can be recycled to Ti(N[R]Ar)(3) in 73% yield by reduction with sodium amalgam, was recovered in 71% yield. WCl3 (THF), was characterized by elemental analysis, SQUID magnetic susceptibility measurements, H-1 NMR spectroscopy and single crystal X-ray crystallography. WCl3 (THF)(3) was found to be an octahedral complex possessing a meridional arrangement of ligands, as has been seen for other MCl3 (THF)(3) complexes (M = Sc, Ti, V, Cr, Mo). (C) 1998 Elsevier Science S.A. All rights reserved.
• A Diamagnetic Dititanium(III) Paddlewheel Complex with No Direct Metal−Metal Bond
  作者：Arjun Mendiratta、Christopher C. Cummins、F. Albert Cotton、Sergey A. Ibragimov、Carlos A. Murillo、Dino Villagrán

  DOI：10.1021/ic0602650

  日期：2006.5.1

  Reaction of Ti[N(Bu-t) Ar](3) (Ar = 3,5-C6H3Me2 or Ar' = C6H5) with CO2 at - 40 degrees C produces diamagmetic Ti-III paddlewheel complexes with long Ti - Ti separations (> 3.4 angstrom), thus excluding direct Ti - Ti bonding. H-1 NMR spectroscopy shows that the compounds are diamagnetic in solution in the temperature range of - 65 to + 70 degrees C. In the solid state, the diamagnetism was found to persist between 2 and 300 K. Calculations at the density functional theory level suggest that the diamagnetism results from antiferromagnetic coupling by superexchange through the ligand pi system.
• Assembly of Molybdenum/Titanium μ-Oxo Complexes via Radical Alkoxide C−O Cleavage
  作者：Jonas C. Peters、Adam R. Johnson、Aaron L. Odom、Paulus W. Wanandi、William M. Davis、Christopher C. Cummins

  DOI：10.1021/ja960564w

  日期：1996.1.1

  Three-coordinate Ti(NRAr)3 [R = C(CD3)2(CH3), Ar = C6H3Me2] was prepared in 73% yield by sodium amalgam reduction of ClTi(NRAr)3 and in 83% yield upon treatment of TiCl3(THF)3 with 3 equiv of Li(NRAr)(OEt2) in the presence of TMEDA. Ti(tBuNPh)3 was prepared similarly in 75% yield by treatment of TiCl3(THF)3 with 3 equiv of Li(tBuNPh)(OEt2) in the presence of TMEDA. Reaction of Ti(NRAr)3 with NMo(OtBu)3 in hydrocarbon

  三配位 Ti(NRAr)3 [R = C(CD3)2(CH3), Ar = C6H3Me2] 通过钠汞齐还原 ClTi(NRAr)3 以 73% 的产率制备，在 TiCl3( THF)3 与 3 当量的 Li(NRAr)(OEt2) 在 TMEDA 存在下。在 TMEDA 存在下，通过用 3 当量的 Li(tBuNPh)(OEt2) 处理 TiCl3(THF)3，类似地制备了 Ti(tBuNPh)3，产率为 75%。Ti(NRAr)3 与 NMo(OtBu)3 在烃溶剂中在 -35 °C 下反应生成一种热不稳定的中间体，公式为 (tBuO)3Mo[μ-N]Ti(NRAr)3，它很容易失去叔丁基自由基并在 25 °C 下异构化。后一个过程的动力学是在 20-60 °C 的温度范围内获得的；该过程表现出干净的一阶行为。获得以下活化参数：ΔH⧧ = 21.4 ± 0.2 kcal mol-1 和