[(2,6-(i-Pr)2C6H3NC(t-Bu)CHC(t-Bu)N-2,6-(i-Pr)2C6H3)ScCl2] | 241165-09-3

• 英文名称: [(2,6-(i-Pr)2C6H3NC(t-Bu)CHC(t-Bu)N-2,6-(i-Pr)2C6H3)ScCl2]
• 英文别名: ((2,6-iPr2-C6H3)NC(tBu)CHC(tBu)N(2,6-iPr2-C6H3))ScCl2
• CAS: 241165-09-3
• 化学式: C₃₅H₅₃Cl₂N₂Sc
• 分子量: 617.681
• InChiKey: ORPPKEPZZIQMLZ-HHHMVCBXSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(2,6-(i-Pr)2C6H3NC(t-Bu)CHC(t-Bu)N-2,6-(i-Pr)2C6H3)ScCl2] 以 甲苯 为溶剂， 生成 [(2,6-diisopropylphenyl)NC(t-Bu)CHC(t-Bu)N(2,6-diisopropylphenyl)]Sc(Me)(NH-t-Bu)
  参考文献：
  名称：

  β-二酮基ina化学：主要酰胺基烷基衍生物的合成，表征和热行为

  摘要：

  的β二酮亚胺基支持钪酰氯的治疗{[ArNC（R）CHC（R）NAR] SCCL 2 } Ñ（AR = 2,6-我镨2 -C 6 H ^ 3 ; R = CH 3，1A，Ñ＝ 2； R ＝t Bu，1b，n＝ 1）和1当量的氨基锂锂试剂LiN（H）R′（R′＝t Bu，2，6 - i Pr 2 -C 6 H 3）得到dium。酰胺衍生物。对于1a，使用LiN（H）t Bu会生成双酰胺基衍生物（6a），而不考虑所用酰胺试剂的当量，这表明当配体是体积较小的甲基取代的实例时，容易进行的配体再分配过程是有效的。对于1b，以高收率获得单酰氨基氯化物2b（R'= t Bu）和3b（R'= 2,6- i Pr 2 -C 6 H 3），这些化合物可用MeLi烷基化以提供单酰胺基甲基化合物4b（R'= t Bu）和5b（R'= 2,6- i Pr 2 -C 6 H 3）。所有这四种化合物均通过晶体学表征。酰胺

  DOI：

  10.1021/om034345c
• 作为产物：
  描述：

  scandium trichloride*3tetrahydrofuran 、 以 甲苯 为溶剂， 以77%的产率得到[(2,6-(i-Pr)2C6H3NC(t-Bu)CHC(t-Bu)N-2,6-(i-Pr)2C6H3)ScCl2]
  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

• Synthesis and Reactivity of a Terminal Scandium Imido Complex
  作者：Terry Chu、Warren E. Piers、Jason L. Dutton、Masood Parvez

  DOI：10.1021/om300913d

  日期：2013.3.11

  Preparation of a terminal scandium imido complex, 2·DMAP, was accomplished through thermolysis of an arylamido methyl complex, 1, stabilized by a bulky β-diketiminato ligand in the presence of 4-N,N-dimethylaminopyridine (DMAP). Mechanistic studies revealed that the reaction proceeds by initial metalation of 1, followed by rapid DMAP-promoted alkane elimination to generate the scandium imido complex. Kinetic

  通过在4- N，N-二甲基氨基吡啶（DMAP）存在下，通过庞大的β-二酮亚胺基配体稳定的芳酰胺基甲基配合物1的热解，完成了末端scan亚氨基配合物2 ·DMAP的制备。机理研究表明，反应首先通过1的金属化进行，然后通过快速DMAP促进的烷烃消除生成generate亚胺基络合物。在拟一级反应条件下，分别合成的金属化物3与DMAP之间反应的动力学研究得出了ΔH的活化参数⧧ = 73.5（2）kJ mol –1和ΔS⧧ = −70.4（5）JK –1 mol –1。2 ·DMAP与叔丁胺或苯乙炔的反应分别在across酰亚胺键上增加了N–H或C–H键，从而提供了络合物内- /外--4和内--5。对这些化合物进行了充分表征，包括通过结构分析，为末端scan亚氨基衍生物2 ·DMAP提供了进一步的证据。
• Accelerated Ligand Metalation in a β-Diketiminato Scandium Dimethyl Complex Activated with Bis(pentafluorophenyl)borane
  作者：Korey D. Conroy、Paul G. Hayes、Warren E. Piers、Masood Parvez

  DOI：10.1021/om700435v

  日期：2007.8.1

  (Ar)NC(tBu)CHC(tBu)N(Ar); Ar = 2,6-iPr2-C6H3) and HB(C6F5)2 proceed through an isolable ion pair 2 to a metalated scandium borate 3 with loss of methane. Multinuclear NMR experiments confirm the proposed structure, which was also verified by synthesis via alternative routes and derivatization. Deuterium labeling studies offer insight into the mechanism of methane loss, which occurs through C−H activation of an

  LScMe 2（L =（Ar）NC（t Bu）CHC（t Bu）N（Ar）; Ar = 2,6- i Pr 2 -C 6 H 3）和HB（C 6 F 5）2的等摩尔反应通过可分离的离子对2到达金属化的硼酸3 3损失甲烷。多核NMR实验证实了所提出的结构，该结构也通过其他途径的合成和衍生化得到了验证。氘标记研究提供了甲烷损失的机理的信息，甲烷的损失是通过C-H活化一种抽象的甲基化物而不是通常的β-二酮亚胺基alkyl络合物通常观察到的直接分子内金属化而发生的。对于2的分解，观察到k H / k D = 8.7（6）的大的主要动力学同位素效应，这证实了所提出的机理，同时还暗示了高反应性的四元Scandocycle中间体LSc（（H）CH 2 B （C 6 F 5）2）。2当量HB（C中的反应6 ˚F 5）2与LSCR 2个产率μ 2种-hydridoborate配合物[LScCH 3 ] [（μ-H）2
• 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.
• Nucleophilic Degradation of a β-Diketiminato Ancillary by a Transient Scandium Hydride Intermediate
  作者：Korey D. Conroy、Warren E. Piers、Masood Parvez

  DOI：10.1021/om900700d

  日期：2009.11.9

  Reactions of a beta-diketiminato-supported scandium dichloride LScCl2 (L = (Ar)NC((BU)-B-t)CHC(Bu-t)N(Ar); Ar = 2,6-u(i)Pr(2)-C6H3) with boro- and aluminohydride reagents result in transient scandium hydrides, which undergo hydride transfer to the ligand backbone, inducing fragmentation of the ancillary. The products of this fragmentation have been characterized and include an organic enamine (2) and scandium imido containing clusters. One such product, formed via reaction with LiBEt3H and LScCl2 is the trimer [ArNScCl(THF)](3)[LiH(THF)], 1, which includes an occluded molecule of lithium hydride. The reactions involving LiAlH4, along with labeling studies, helped to clarify the fragmentation pathway and account for the observed products.