(1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato)TiCl₃ | 1158589-57-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: (1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato)TiCl₃
• 英文别名: (Im^DippN)TiCl₃；[1,3-Bis[2,6-di(propan-2-yl)phenyl]imidazol-2-ylidene]azanide;titanium(4+);trichloride；[1,3-bis[2,6-di(propan-2-yl)phenyl]imidazol-2-ylidene]azanide;titanium(4+);trichloride
• CAS: 1158589-57-1
• 化学式: C₂₇H₃₆Cl₃N₃Ti
• 分子量: 556.842
• InChiKey: CYVLQSFMNHAKIT-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  -1.76
• 重原子数：
  34
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  7.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato)TiCl₃ 、 Potassium cyclooctatetraene dianion 以 四氢呋喃 为溶剂， 以64%的产率得到[(η8-cycloctatetraenide)TiCl(1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato)]
  参考文献：
  名称：

  Imidazolin-2-iminato Complexes of Rare Earth Metals with Very Short Metal−Nitrogen Bonds: Experimental and Theoretical Studies

  摘要：

  The reactions of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(DiPP)NH, 1-H) with trimethylsilylmethyl lithium (LiCH2SiMe3) and anhydrous rare earth metal trichlorides MCl3 afforded the imidazolin-2-iminato complexes [(1)MCl2(THF)(3)] (2a, M = Sc; 2b, M = Y; 2c, M = Lu) and [(1)GdCl2(THF)(2)]center dot[LiCl(THF)(2)] (2d). Treatment of complexes 2 with dipotassium cyclooctatetradienide, K-2(C8H8) resulted in the formation of two- or three-legged pianostool complexes of the type [(eta(8)-C8H8)M(1)(THF)(n)] (3a, M = Sc, n = 1; 3b, M = Y, n = 2; 3c, M = Lu, n = 2; 3d, M = Gd, n = 2). X-ray diffraction analyses of all eight complexes 2 and 3 revealed the presence of very short metal-nitrogen bonds, which are among the shortest ever observed for these elements. [(eta(8)-C8H8)Sc(1)(THF)] (3a) reacted with 2,6-dimethylphenyl isothiocyanate (Xy-NCS) to form the [2 + 2]-cycloaddition product 4, which contains a thioureato-N, N' moiety. The related COT-titanium complex [(eta(8) -C8H8)TiCl(1)] (6) could be obtained from [(1)TiCl3] (5) by reaction with K-2(C8H8) and was structurally characterized, As a theoretical analysis of the nature of the metal-nitrogen bond, density functional theory (DFT) calculations have been carried out for complexes 3a and 6 and also for the model complexes [(eta(8)-C8H8)Sc(Nlm(Me))] (7), [(eta(8)-C8H8)Ti(Nlm(Me))](+) (8), and [(eta(8)-C8H8)Ti (NXy)] (9), revealing a marked similarity of the bonding in imidazolin-2-iminato and conventional imido metal complexes.

  DOI：

  10.1021/ic900503q
• 作为产物：
  描述：

  1,3-bis(2,6-diisopropylphenyl)-2-(trimethylsilylimino)imidazoline 、 四氯化钛 以 正己烷 为溶剂， 以95%的产率得到(1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato)TiCl₃
  参考文献：
  名称：

  Imidazolin-2-iminato Complexes of Rare Earth Metals with Very Short Metal−Nitrogen Bonds: Experimental and Theoretical Studies

  摘要：

  The reactions of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(DiPP)NH, 1-H) with trimethylsilylmethyl lithium (LiCH2SiMe3) and anhydrous rare earth metal trichlorides MCl3 afforded the imidazolin-2-iminato complexes [(1)MCl2(THF)(3)] (2a, M = Sc; 2b, M = Y; 2c, M = Lu) and [(1)GdCl2(THF)(2)]center dot[LiCl(THF)(2)] (2d). Treatment of complexes 2 with dipotassium cyclooctatetradienide, K-2(C8H8) resulted in the formation of two- or three-legged pianostool complexes of the type [(eta(8)-C8H8)M(1)(THF)(n)] (3a, M = Sc, n = 1; 3b, M = Y, n = 2; 3c, M = Lu, n = 2; 3d, M = Gd, n = 2). X-ray diffraction analyses of all eight complexes 2 and 3 revealed the presence of very short metal-nitrogen bonds, which are among the shortest ever observed for these elements. [(eta(8)-C8H8)Sc(1)(THF)] (3a) reacted with 2,6-dimethylphenyl isothiocyanate (Xy-NCS) to form the [2 + 2]-cycloaddition product 4, which contains a thioureato-N, N' moiety. The related COT-titanium complex [(eta(8) -C8H8)TiCl(1)] (6) could be obtained from [(1)TiCl3] (5) by reaction with K-2(C8H8) and was structurally characterized, As a theoretical analysis of the nature of the metal-nitrogen bond, density functional theory (DFT) calculations have been carried out for complexes 3a and 6 and also for the model complexes [(eta(8)-C8H8)Sc(Nlm(Me))] (7), [(eta(8)-C8H8)Ti(Nlm(Me))](+) (8), and [(eta(8)-C8H8)Ti (NXy)] (9), revealing a marked similarity of the bonding in imidazolin-2-iminato and conventional imido metal complexes.

  DOI：

  10.1021/ic900503q

文献信息

• Titanium‐Mediated Catalytic Hydrogenation of Monocyclic and Polycyclic Arenes
  作者：Alejandra Gómez‐Torres、J. Rolando Aguilar‐Calderón、Angela M. Encerrado‐Manriquez、Maren Pink、Alejandro J. Metta‐Magaña、Wen‐Yee Lee、Skye Fortier

  DOI：10.1002/chem.201905466

  日期：2020.3.2

  (ImDipp N)(Xyket guan)Ti(η6 -C6 H6 ) (1inter ) (Xyket guan=[(tBuC=N)C(NXylyl)2 ]- , Xylyl=2,5-dimethylphenyl) in the absence or presence of benzene, respectively. These complexes have been found to hydrogenate monocyclic and polycyclic arenes under relatively mild conditions (150 psi, 80 °C)-the first example of catalytic, homogeneous arene hydrogenation with TON >1 by a Group IV system.

  TiIV胍盐配合物（ImDipp N）（Xyket guan）TiCl2的两个电子还原给出（η6-ImDippN）（xyket guan）Ti（1内）和（ImDipp N）（Xyket guan）Ti（η6-C6H6）（ 1inter）（Xyket guan = [（tBuC = N）C（NXylyl）2]-，Xylyl = 2,5-二甲基苯基）分别在不存在或存在苯的情况下。已发现这些络合物在相对温和的条件下（150 psi，80°C）氢化单环和多环芳烃-第IV组通过TON> 1催化均相芳烃加氢的第一个实例。
• Molecular Capacitors: Accessible 6- and 8-Electron Redox Chemistry from Dimeric “Ti(I)” and “Ti(0)” Synthons Supported by Imidazolin-2-Iminato Ligands
  作者：Alejandra Gómez-Torres、Niki Mavragani、Alejandro Metta-Magaña、Muralee Murugesu、Skye Fortier

  DOI：10.1021/acs.inorgchem.2c02881

  日期：2022.10.24

  aromatic system most consistent with two-electron reduction of the ring. As such, 2 and 3 can be assigned respectively as possessing metal centers in formal Ti(III)/Ti(III) and Ti(II)/Ti(II) oxidation states. Exploration of their redox chemistry reveal the ability to reduce several substrate equivalents. For instance, treatment of 2 with excess C8H8 (COT) forms the novel COT-bridged complex [(ImDippN)(η8-

  还原抗磁性 Ti(III)/Ti(III) 二聚体 [Cl 2 Ti(μ- NIm Dipp )] 2 ( 1 ) ( NIm Dipp = [1,3-bis(Dipp)imidazolin-2-iminato] - , Dipp = C 6 H 3 -2,6- i Pr 2 ) 与 4 和 6 equiv 的 KC 8生成分子内芳烃掩蔽的双核钛化合物 [(μ-N-η 6 -Im Dipp )Ti] 2 ( 2 ) 和 [(Et 2 O) 2 K](μ-N-μ -η 6 :η 6 -Im Dipp )Ti}2 ( 3 )，分别以适度的产量。通过 X 射线晶体学分析对化合物的结构进行了表征，对桥连咪唑啉-2-亚氨基配体的 η 6配位芳基取代基内的键度数的检查表明，芳族系统的扰动与二电子还原最一致戒指。因此，2和3可以分别指定为具有形式 Ti(III)/Ti(III) 和 Ti(II)/Ti(II)
• Imidazolin-2-iminato Complexes of Rare Earth Metals with Very Short Metal−Nitrogen Bonds: Experimental and Theoretical Studies
  作者：Tarun K. Panda、Alexandra G. Trambitas、Thomas Bannenberg、Cristian G. Hrib、Sören Randoll、Peter G. Jones、Matthias Tamm

  DOI：10.1021/ic900503q

  日期：2009.6.15

  The reactions of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(DiPP)NH, 1-H) with trimethylsilylmethyl lithium (LiCH2SiMe3) and anhydrous rare earth metal trichlorides MCl3 afforded the imidazolin-2-iminato complexes [(1)MCl2(THF)(3)] (2a, M = Sc; 2b, M = Y; 2c, M = Lu) and [(1)GdCl2(THF)(2)]center dot[LiCl(THF)(2)] (2d). Treatment of complexes 2 with dipotassium cyclooctatetradienide, K-2(C8H8) resulted in the formation of two- or three-legged pianostool complexes of the type [(eta(8)-C8H8)M(1)(THF)(n)] (3a, M = Sc, n = 1; 3b, M = Y, n = 2; 3c, M = Lu, n = 2; 3d, M = Gd, n = 2). X-ray diffraction analyses of all eight complexes 2 and 3 revealed the presence of very short metal-nitrogen bonds, which are among the shortest ever observed for these elements. [(eta(8)-C8H8)Sc(1)(THF)] (3a) reacted with 2,6-dimethylphenyl isothiocyanate (Xy-NCS) to form the [2 + 2]-cycloaddition product 4, which contains a thioureato-N, N' moiety. The related COT-titanium complex [(eta(8) -C8H8)TiCl(1)] (6) could be obtained from [(1)TiCl3] (5) by reaction with K-2(C8H8) and was structurally characterized, As a theoretical analysis of the nature of the metal-nitrogen bond, density functional theory (DFT) calculations have been carried out for complexes 3a and 6 and also for the model complexes [(eta(8)-C8H8)Sc(Nlm(Me))] (7), [(eta(8)-C8H8)Ti(Nlm(Me))](+) (8), and [(eta(8)-C8H8)Ti (NXy)] (9), revealing a marked similarity of the bonding in imidazolin-2-iminato and conventional imido metal complexes.