(4,4''-dimethyl-[1,1':3',1''-terphenyl]-2'-yl)lithium | 1005397-79-4

• 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: (4,4''-dimethyl-[1,1':3',1''-terphenyl]-2'-yl)lithium
• CAS: 1005397-79-4
• 化学式: C₂₀H₁₇Li
• 分子量: 264.296
• InChiKey: CWBQNTQNHQHZHA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.43
• 重原子数：
  21.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (4,4''-dimethyl-[1,1':3',1''-terphenyl]-2'-yl)lithium 、 [Ta(NMe2)3Cl2]2 以 乙醚 为溶剂， 反应 0.58h， 以28%的产率得到1,3-bis(4-methylphenyl)benzene-2-ide;dimethylazanide;tantalum(5+);chloride
  参考文献：
  名称：

  Synthesis, Structural Characterization, and Cyclometalation Chemistry of Tantalum Terphenyl Compounds

  摘要：

  The kappa(1)-m-terphenyl complex of tantalum, [Ar-Tol2]Ta-(NMe2)(3)Cl ([Ar-Tol2] = 2,6-di-p-tolylphenyl), has been synthesized by the reaction of [Ta(NMe2)(3)Cl-2](2) with two equivalents of [Ar-Tol2]Li. [Ar-Tol2]Ta(NMe2)(3)Cl provides access to a variety of monoalkyl compounds, [Ar-Tol2]Ta(NMe2)(3)R (R = Me, Et, Pr-n, Bu-n, and Np; Np = CH2But), via the reactions with the corresponding RLi. In addition, the reaction of [Ta(NMe2)(3)Cl-2](2) with excess [Ar-Tol2]Li affords the bis(terphenyl) complex, [Ar-Tol2](2)Ta(NMe2)(3), while the reaction of [Ar-Tol2]Ta(NMe2)(3)Cl with LiBH4 gives the borohydride complex, [Ar-Tol2]Ta(NMe2)(3)(kappa(2)-BH4). The dichloride compound, [Ar-Tol2]Ta(NMe2)(2)Cl-2, which is obtained via the reaction of [Ar-Tol2]Ta(NMe2)(3)Cl with Me3SiCl, provides access to a series of dialkyl derivatives, [Ar-Tol2]Ta(NMe2)(2)R-2 (R = Me, Et, Prn, Bun, and Np), via the reactions with the corresponding RLi. The kappa(1)-m-terphenyl ligands in these complexes are susceptible to metalation. Thus, [Ar-Tol2]Ta(NMe2)(3)R eliminates RH to afford [kappa(2)-Ar-Tol,Ar-Tol']Ta(NMe2)(3) (Tol' = C6H3Me), while [Ar-Tol2]Ta(NMe2)(2)Np-2 eliminates NpH to form [kappa(2)-Ar-Tol,Ar-Tol']Ta(NMe2)(2)Np.

  DOI：

  10.1021/acs.organomet.5b00158

文献信息

• A New Class of Transition Metal Pincer Ligand: Tantalum Complexes that Feature a [<i>CCC</i>] X₃-Donor Array Derived from a Terphenyl Ligand
  作者：Aaron Sattler、Gerard Parkin

  DOI：10.1021/ja210404x

  日期：2012.2.1

  A new class of [CCC] X-3-donor pincer ligand for transition metals has been constructed via cyclometalation of a 2,6-di-p-tolylphenyl ([Ar-Tol2]) derivative. Specifically, addition of PMe3 to [Ar-Tol2]TaMe3Cl induces elimination of methane and formation of the pincer complex, [kappa(3)-Ar-Tol2]-Ta(PMe3)(2)MeCl (Tol' = C6H3Me), which may also be obtained by treatment of Ta(PMe3)(2)Me3Cl2 with [Ar-Tol2]Li. Solutions of [kappa(3)-Ar-Tol2]Ta(PMe3)(2)MeCl undergo ligand redistribution with the formation of [kappa(3)-Ar-Tol2]Ta(PMe3)(2)Me-2 and [kappa(3)-Ar-Tol2]Ta(PMe3)(2)Cl-2, which may also be synthesized by the reactions of [kappa(3)-Ar-Tol2]Ta(PMe3)(2)MeCl with MeMgBr and ZnCl2, respectively. Reduction of [kappa(3)-Ar-Tol2]Ta(PMe3)(2)Cl-2 with KC8 in benzene gives the benzene complex [kappa(3)-Ar-Tol2]-Ta(PMe3)(2)(eta(6)-C6H6) that is better described as a 1,4-cyclohexadienediyl derivative. Deuterium labeling employing Ta(PMe3)(2)-(CD3)(3)Cl-2 demonstrates that the pincer ligand is created by a pair of Ar-H/Ta-Me sigma-bond metathesis transformations, rather than by a mechanism that involves alpha-H abstraction by a tantalum methyl ligand.