[(1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato)GdCl(THF)2LiCl(THF)2] | 1158589-72-0

• 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)GdCl(THF)2LiCl(THF)2]
• 英文别名: lithium;[1,3-bis[2,6-di(propan-2-yl)phenyl]imidazol-2-ylidene]azanide;gadolinium(3+);oxolane;trichloride
• CAS: 1158589-72-0
• 化学式: C₄₃H₆₈Cl₃GdLiN₃O₄
• 分子量: 961.581
• InChiKey: ZNRLMOWCNIGIDB-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  -1.57
• 重原子数：
  55
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  44.4
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  [(1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato)GdCl(THF)2LiCl(THF)2] 、 Potassium cyclooctatetraene dianion 以 四氢呋喃 为溶剂， 以79%的产率得到[(η8-cycloctatetraenide)Gd(1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato)(THF)2]*THF
  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：

  四氢呋喃 、 bis(2,6-diisopropylphenyl)imidazolin-2-imine 、 氯化钆 、 trimethylsilylmethyllithium 以 四氢呋喃 为溶剂， 以73%的产率得到[(1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato)GdCl(THF)2LiCl(THF)2]
  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

• Rare-Earth Metal Alkyl, Amido, and Cyclopentadienyl Complexes Supported by Imidazolin-2-iminato Ligands: Synthesis, Structural Characterization, and Catalytic Application
  作者：Alexandra G. Trambitas、Tarun K. Panda、Jelena Jenter、Peter W. Roesky、Constantin Daniliuc、Cristian G. Hrib、Peter G. Jones、Matthias Tamm

  DOI：10.1021/ic9024052

  日期：2010.3.1

  [(1)MCl2(THF)3] (2a, M = Sc; 2b, M = Y; 2c, M = Lu) and the gadolinium complex [(1)GdCl2(THF)2]·[LiCl(THF)2] (2d), containing the 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato ligand 1, proved to be versatile starting materials for the preparation of trimethylsilylmethyl (“neosilyl”) and bis(trimethylsilyl)amido complexes [(1)M(CH2SiMe3)2(THF)2] (3a−3d) and [(1)M(HMDS)2(THF)] [4a−4d, HMDS = hexamethyldisilazide

  稀土金属二氯化物[（1）MCl 2（THF）3 ]（2a，M = Sc; 2b，M = Y; 2c，M = Lu）和complex配合物[（1）GdCl 2（THF）2 ] ·含有1,3-双（2,6-二异丙基苯基）咪唑啉-2-亚氨基配体1的[LiCl（THF）2 ]（2d）被证明是制备三甲基甲硅烷基甲基（“新甲硅烷基”）的通用原料和双（三甲基甲硅烷基）酰胺基络合物[（1）M（CH 2 SiMe 3）2（THF）2 ]（3a- 3D）和[（1）M（HMDS）2（THF）] [ 4A - 4D，HMDS =六甲基二硅，N（森达3）2 ]和苄基配合物的制备[（1）路（CH 2博士）2（THF）2 ]（5c），分别与LiCH 2 SiMe 3，Na [N（SiMe 3）2 ]和KCH 2 Ph反应。用KCp *处理2a - 2c得到单（五甲基环戊二烯基）络合物[（1）Sc（Cp *）Cl（THF）]（6a），[（1）Y（Cp