([N,N'-bis(3-dimethylaminopropyl)-4,5-dimethoxybenzene-1,2-diamine(2-)]Ti(μ-p-NC6H4Me))2 | 1259333-38-4

• 英文名称: ([N,N'-bis(3-dimethylaminopropyl)-4,5-dimethoxybenzene-1,2-diamine(2-)]Ti(μ-p-NC6H4Me))2
• CAS: 1259333-38-4
• 化学式: C₅₀H₇₈N₁₀O₄Ti₂
• 分子量: 978.994
• InChiKey: VCHFAQQALDWIRL-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  [N,N'-bis(3-dimethylaminopropyl)-4,5-dimethoxybenzene-1,2-diamine(2-)]TiCl2 、 乙烷,三氯氟- 在 KH 作用下， 以 四氢呋喃 为溶剂， 以65%的产率得到([N,N'-bis(3-dimethylaminopropyl)-4,5-dimethoxybenzene-1,2-diamine(2-)]Ti(μ-p-NC6H4Me))2
  参考文献：
  名称：

  Steric and Electronic Consequences of Flexibility in a Tetradentate Redox-Active Ligand: Ti(IV) and Zr(IV) Complexes

  摘要：

  A redox-active, tetradentate ligand, N,N'-bis-(3-dimethylamino-propyl)-4,5-dimethoq-benzene-1,2-diamide ([N2N2cat](2-)), was developed, and the six-coordinate metal complexes [N2N2cat]TiCl2 (3) and [N2N2cat]ZrCl2 (4) were synthesized. The tetradentate ligand was determined to be fluxional in 3 and 4, enabled by reversible dissociation of the neutral amine groups of the [N2N2cat](2-) ligand. Both amine arms of 3 could be replaced by N,N-dimethylaminopyridine with an overall free energy change of -4.64(3) kcal mol(-1) at 298 K. Cyclic voltammetry experiments were used to probe the redox capabilities of the [N2N2cat](2-) ligand: complex 3 exhibited two one-electron oxidations at -0.19 and -0.52 V versus [Cp2Fe](+/0) while 4 exhibited a single two-electron oxidation at 0.55 V. Substitution of the chlorides in 3 for an imide afforded the dimer {[N2N2cat]Ti(mu-p-NC6H4Me)}(2), in which the metal centers are five-coordinate because of dissociation of one amine arm of the [N2N2cat](2-) ligand. While the bis-azide complex [N2N2cat]Ti(N-3)(2) was stable toward elimination of N-2, the bis-phenylacetylide complex [N2N2cat]Ti(C CPh)(2) could be oxidized by PhICl2, resulting in subsequent reductive elimination of 1,4-diphenybutadiyne.

  DOI：

  10.1021/ic101468p