(Nacnac)ScCl2(THF) | 241165-08-2

• 英文名称: (Nacnac)ScCl2(THF)
• 英文别名: (2,6-(CH(CH3)2)2C6H3NC(CH3)CHC(CH3)N-2,6-(CH(CH3)2)2C6H3)ScCl2(THF)
• CAS: 241165-08-2
• 化学式: C₃₃H₄₉Cl₂N₂OSc
• 分子量: 605.627
• InChiKey: BSUIWVGVLFJSDU-ISTOKIOSSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• 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：

  (Nacnac)ScCl2(THF) 以 氘代甲苯 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Dialkylscandium Complexes Supported by β-Diketiminato Ligands:  Synthesis, Characterization, and Thermal Stability of a New Family of Organoscandium Complexes

  摘要：

  Several diorganoscandium complexes stabilized by the beta -diketiminato ligands (Ar)NC(R)CHC(R)N(Ar) (Ar = 2,6-iPr-C6H3; R = CH3 (ligand a), R = rBu (ligand b)) have been synthesized. Reaction of the lithium salts of the ligands with ScCl3. 3THF leads to the complexes LScCl2(THF)(n), which may be readily alkylated to form the dialkyl derivatives. Most are isolated as base-free, four-coordinate complexes. Several have been characterized via X-ray crystallography, and a detailed discussion of their structures is presented. Steric interactions between Ar and the Sc-alkyl groups force the scandium to adopt an out-of-plane bonding mode. In solution, this is manifested via a fluxional process which equilibrates the two diastereotopic alkyl groups and ligand groups as well. The barriers to this process roughly correlate with the steric bulk of the alkyl substituents. At elevated temperatures, the dialkyl derivatives LScR2 undergo a metalation process whereby one of the alkyl groups is eliminated as RH, and a ligand iPr group is metalated in the methyl position. These reactions are first order in scandium complex, and activation parameters of DeltaH(double dagger) = 19.7(6) kcal mol(-1) and DeltaS(double dagger) = -17(2) cal mol(-1) K-1 were measured for the loss of Me4Si from (Ligb)Sc(CH2SiMe3)(2).

  DOI：

  10.1021/om010131o
• 作为产物：
  描述：

  Li(2,6-iPr2C6H3)NC(Me)CHC(Me)N(2,6-iPr2C6H3) 、 scandium trichloride*3tetrahydrofuran 以 甲苯 为溶剂， 生成 (Nacnac)ScCl2(THF)
  参考文献：
  名称：

  Dialkylscandium Complexes Supported by β-Diketiminato Ligands:  Synthesis, Characterization, and Thermal Stability of a New Family of Organoscandium Complexes

  摘要：

  Several diorganoscandium complexes stabilized by the beta -diketiminato ligands (Ar)NC(R)CHC(R)N(Ar) (Ar = 2,6-iPr-C6H3; R = CH3 (ligand a), R = rBu (ligand b)) have been synthesized. Reaction of the lithium salts of the ligands with ScCl3. 3THF leads to the complexes LScCl2(THF)(n), which may be readily alkylated to form the dialkyl derivatives. Most are isolated as base-free, four-coordinate complexes. Several have been characterized via X-ray crystallography, and a detailed discussion of their structures is presented. Steric interactions between Ar and the Sc-alkyl groups force the scandium to adopt an out-of-plane bonding mode. In solution, this is manifested via a fluxional process which equilibrates the two diastereotopic alkyl groups and ligand groups as well. The barriers to this process roughly correlate with the steric bulk of the alkyl substituents. At elevated temperatures, the dialkyl derivatives LScR2 undergo a metalation process whereby one of the alkyl groups is eliminated as RH, and a ligand iPr group is metalated in the methyl position. These reactions are first order in scandium complex, and activation parameters of DeltaH(double dagger) = 19.7(6) kcal mol(-1) and DeltaS(double dagger) = -17(2) cal mol(-1) K-1 were measured for the loss of Me4Si from (Ligb)Sc(CH2SiMe3)(2).

  DOI：

  10.1021/om010131o

文献信息

• Cationic Organoscandium β-Diketiminato Chemistry:  Arene Exchange Kinetics in Solvent Separated Ion Pairs
  作者：Paul G. Hayes、Warren E. Piers、Masood Parvez

  DOI：10.1021/ja034680s

  日期：2003.5.1

  Abstraction of methide from the beta-diketiminato supported organoscandium complex [L1ScMe2]2 using the trityl borate activator [Ph3C][B(C6F5)4] in arene solvents gives solvent separated ion pairs in which the arene (C6H5Br, 1a; C6H6, 1b; C7H8, 1c; 1,3,5-Me3C6H3, 1d) is coordinated to the cationic scandium center in an eta6 bonding mode. L1 incorporates methyl groups in the 2,4 positions of the ligand

  使用芳烃溶剂中的硼酸三苯甲基活化剂 [Ph3C][B(C6F5)4] 从 β-二酮亚胺基支持的有机钪络合物 [L1ScMe2]2 中提取甲基化物，得到溶剂分离的离子对，其中芳烃 (C6H5Br, 1a; C6H6, 1b ; C7H8, 1c; 1,3,5-Me3C6H3, 1d) 以 eta6 键合模式与阳离子钪中心配位。L1 在配体骨架的 2,4 位结合了甲基，在氮原子上结合了庞大的 2,6-二异丙基苯基。芳烃的相对结合强度为 < < 1,3,5-Me3C6H3 < 。离子对 1a 和 1c 已在晶体学上进行了表征， 衍生物以其 eta6 键合模式而不是通过卤素原子的更常见 eta1 键合模式而著称。甲苯置换均三甲苯的动力学(1d --> 1c) DeltaH = 21.4(6) kcal mol-1 和 DeltaS = 6(1) cal mol-1
• A Scandium‐Stabilized Diisophosphaethynolate Ligand: [OCPPCO] ⁴⁻
  作者：Lauren N. Grant、Balazs Pinter、Brian C. Manor、Hansjörg Grützmacher、Daniel J. Mindiola

  DOI：10.1002/anie.201710757

  日期：2018.1.22

  The first example of the OCPPCO ligand, diisophosphaethynolate, is reported via reductive coupling of a Sc−OCP precursor. Upon reduction with KC8, isolation of the dinuclear complex, namely [K(OEt2)]2[(nacnac)Sc(OAr)]2(OCPPCO), is observed, leading to a unique motif [OCPPCO]4−, stabilized by two scandium centers. Detailed NMR spectra of all complexes as well as IR and single crystal X‐ray studies were

  OCPPCO配体的第一个例子，二异磷酸胸腺嘧啶，是通过Sc-OCP前体的还原偶联而报告的。用KC 8还原后，观察到双核复合物，即[K（OEt 2）] 2 [（nacnac）Sc（OAr）] 2（OCPPCO）的分离，从而导致稳定的独特基序[OCPPCO] 4−由两个scan中心。获得了所有配合物的详细NMR光谱以及IR和单晶X射线研究，以充分阐明溶液和固态时这些配合物的性质。结合理论以探讨负责Sc-OCPPCO-Sc骨架中键合相互作用的电子结构和轨道，还可以与在前体中观察到的线性模式进行比较。
• Carbon−Oxygen Bond Cleavage Promoted by a Scandium Borohydride Complex
  作者：Falguni Basuli、John Tomaszewski、John C. Huffman、Daniel J. Mindiola

  DOI：10.1021/om030374b

  日期：2003.11.1

  Treatment of (Nacnac)ScCl2(THF) (Nacnac(-) = ArNC(CH3)CHC(CH3)NAr, Ar = 2,6-(CH(CH3)(2))(2)C6H3) with KNHAr in THF affords in 83% yield the chloro-anilide complex (Nacnac)ScCl(NHAr)(THF) (1-Cl(THF)). 1-Cl(THF) was fully characterized, and a single-crystal X-ray diffraction study reveals the complex to be a five-coordinate scandium complex containing a bound THF ligand. The complex 1-Cl(THF) reacts cleanly with NaBHEt3 in toluene to yield the triethylborohydride adduct (Nacnac)Sc(NHAr)(HBEt3) (1-HBEt3) in 78% yield. The molecular structure of 1-HBEt3 indicated a bridged hydride ligand confined between the scandium and boron atoms. The coordination environment of scandium was that of an octahedron, with the two remaining coordination sites being occupied by one hydrogen from each methylene group on the borane interacting with the scandium center through agostic interactions. Variable-temperature B-11 NMR spectroscopy indicated a doublet with J(BH) = 53 Hz (70 degreesC). Borane extrusion in the complex 1-HBEt3 in Et2O affords the ethoxide (Nacnac)Sc(NHAr)(OEt) (1-OEt), which was structurally characterized. Tetrahydrofuran also reacts cleanly with 1-HBEt3 to yield the enolate complex (Nacnac)Sc(NHAr)(OCH=CH2) (1-OCH=CH2) in 70% yield. The molecular structure of 1-OCH=CH2 was also determined by single-crystal X-ray diffraction methods. In the absence of Lewis bases such as Et2O or THF, 1-HBEt3 was found to thermally decompose to a mixture of products. When 1 equiv of benzophenone was added to 1-HBEt3, the putative hydride "1-H" was trapped to yield the diphenylmethoxide complex (Nacnac)Sc(NHAr)(OCHPh2) (1-OCHPh2) in 80% yield. As an alternative to 1-HBEt3 cleaving C-O bonds, the stable tert-butyl complex (Nacnac)Sc(NHAr)(Bu-t) (1-Bu-t), prepared in 94% yield from 1-Cl(THF) and solid (LiBu)-Bu-t, was also found to react with Et2O to yield 1-OEt. The complex 1-Bu-t was fully characterized, and the molecular structure was established by single-crystal X-ray diffraction methods. 1-Bu-t was thermally stable in the absence of Et2O and THF.
• Synthesis of Dialkylscandium Complexes Supported by β-Diketiminato Ligands and Activation with Tris(pentafluorophenyl)borane
  作者：Lawrence W. M. Lee、Warren E. Piers、Mark R. J. Elsegood、William Clegg、Masood Parvez

  DOI：10.1021/om9903801

  日期：1999.8.1

  Treatment of ScCl3. THF3 with the lithium salts of the ligands ArNC(R)CHC(R)NAr, where Ar = 2,6-Pr-i-C6H3 and R = CH3 and Bu-t, gives LScCl2. nTHF derivatives (R = CH3, n = 1, 1a; R = Bu-t, n = 0, 1b). These compounds can be derivatized by allylation with methyllithium or benzylpotassium. The dibenzyl compound prepared from 1a, when treated with B(C6F5)(3), gives an ion pair, 4, in which the cationic scandium center is stabilized by a eta(6)-aryl interaction with the abstracted berate benzyl group.