4,4''-diphenyl-6,6''-di(4-ethoxycarbonylphenyl)-2,2':6',2''-terpyridine | 402852-93-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 4,4''-diphenyl-6,6''-di(4-ethoxycarbonylphenyl)-2,2':6',2''-terpyridine
• 英文别名: Ethyl 4-[6-[6-[6-(4-ethoxycarbonylphenyl)-4-phenylpyridin-2-yl]pyridin-2-yl]-4-phenylpyridin-2-yl]benzoate；ethyl 4-[6-[6-[6-(4-ethoxycarbonylphenyl)-4-phenylpyridin-2-yl]pyridin-2-yl]-4-phenylpyridin-2-yl]benzoate
• CAS: 402852-93-1
• 化学式: C₄₅H₃₅N₃O₄
• 分子量: 681.791
• InChiKey: NZHGYBHLHPWDTR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  52
• 可旋转键数：
  12
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  91.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ammonium hexafluorophosphate 、 [trichloro(4'-tolyl-2,2':6',2''-terpyridine)ruthenium(III)] 、 4,4''-diphenyl-6,6''-di(4-ethoxycarbonylphenyl)-2,2':6',2''-terpyridine 在 AgBF₄ 作用下， 以 丙酮 为溶剂， 以61%的产率得到[Ru(4,4''-diphenyl-6,6''-di(4-ethoxycarbonylphenyl)-2,2':6',2''-terpyridine)(4'-p-tolyl-2,2':6',2''-terpyridine)](PF6)2*0.5NH4PF6
  参考文献：
  名称：

  Ru(II) complexes of polyarylated terpyridines: unexpected side-chain C-metallation and photosensitization of electron transfer

  摘要：

  The new ligands 4,4 " -diphenyl-6,6 " -di(4-ethoxycarbonylphenyl)-2,2':6',2 " -terpyridine (H4), its non-carboxylated 4,6,4 " ,6 " -tetraphenyl analogue (H5) and the 4,4 " -diphenyl-6,6 " -di(4-methoxyphenyl) analogue were prepared in high yields via double Krohnke reactions. Reactions with activated (ttpy)RuCl3 (ttpy is 4'-p-tolyl-2,2':6',2 " -terpyridine) provided the symmetrical N-6-coordinated complexes, [Ru(H4)(ttpy)](PF6)(2) and [Ru(H5)(ttpy)](PF6)2, along with the novel, unsymmetrical C-metallated analogues [Ru(4)(ttpy)]PF6 and [Ru(5)(ttpy)]PF6, in which an unprecedented side-chain metallation occurred in lieu of incomplete substitution. A crystallographic analysis of [Ru(5)(ttpy)]NO3 confirmed the N5C donor set in these products and revealed a distorted binding of 5(-) as well as 'pi -stacking' between its uncoordinated pyridine and the ttpy ligand. The diester [Ru(H4)(ttpy)](PF6)(2) was hydrolyzed to the diacid complex [Ru(H(2)3)(ttpy)PF6)(2) (H(2)3 is 4,4 " -diphenyl-6,6 " -di(4-carboxyphenyl)2,2':6',2 " -terpyridine). Measurements of the photogeneration of methyl viologen cation radical with [Ru(H5)(ttpy)](PF6)(2) and [Ru(H(2)3)(ttpy)](PF6)(2) as sensitizers showed that the presence of carboxyl groups in the latter provided a distinct benefit, owing to the formation of the neutral form [Ru(3)(ttpy)](0) but this was insufficient to overcome the detrimental effect of inter-ligand repulsions. (C) 2001 Published by Elsevier Science B.V.

  DOI：

  10.1016/s0020-1693(01)00626-0

文献信息

• Ru(II) complexes of polyarylated terpyridines: unexpected side-chain C-metallation and photosensitization of electron transfer
  作者：Charles Mikel、Pierre G. Potvin

  DOI：10.1016/s0020-1693(01)00626-0

  日期：2001.12

  The new ligands 4,4 " -diphenyl-6,6 " -di(4-ethoxycarbonylphenyl)-2,2':6',2 " -terpyridine (H4), its non-carboxylated 4,6,4 " ,6 " -tetraphenyl analogue (H5) and the 4,4 " -diphenyl-6,6 " -di(4-methoxyphenyl) analogue were prepared in high yields via double Krohnke reactions. Reactions with activated (ttpy)RuCl3 (ttpy is 4'-p-tolyl-2,2':6',2 " -terpyridine) provided the symmetrical N-6-coordinated complexes, [Ru(H4)(ttpy)](PF6)(2) and [Ru(H5)(ttpy)](PF6)2, along with the novel, unsymmetrical C-metallated analogues [Ru(4)(ttpy)]PF6 and [Ru(5)(ttpy)]PF6, in which an unprecedented side-chain metallation occurred in lieu of incomplete substitution. A crystallographic analysis of [Ru(5)(ttpy)]NO3 confirmed the N5C donor set in these products and revealed a distorted binding of 5(-) as well as 'pi -stacking' between its uncoordinated pyridine and the ttpy ligand. The diester [Ru(H4)(ttpy)](PF6)(2) was hydrolyzed to the diacid complex [Ru(H(2)3)(ttpy)PF6)(2) (H(2)3 is 4,4 " -diphenyl-6,6 " -di(4-carboxyphenyl)2,2':6',2 " -terpyridine). Measurements of the photogeneration of methyl viologen cation radical with [Ru(H5)(ttpy)](PF6)(2) and [Ru(H(2)3)(ttpy)](PF6)(2) as sensitizers showed that the presence of carboxyl groups in the latter provided a distinct benefit, owing to the formation of the neutral form [Ru(3)(ttpy)](0) but this was insufficient to overcome the detrimental effect of inter-ligand repulsions. (C) 2001 Published by Elsevier Science B.V.