Ru(2,2':6',2''-terpyridine)(2,6-pyridinedicarboxylate) | 198902-93-1

• 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: Ru(2,2':6',2''-terpyridine)(2,6-pyridinedicarboxylate)
• 英文别名: [Ru(2,2':6',2-terpyridine)(pyridine-2,6-dicarboxylate)]；2,6-Dipyridin-2-ylpyridine;pyridine-2,6-dicarboxylate;ruthenium(2+)
• CAS: 198902-93-1
• 化学式: C₂₂H₁₄N₄O₄Ru
• 分子量: 499.448
• InChiKey: JQSXXIYBTUZEHQ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.01
• 重原子数：
  31
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  132
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Ru(2,2':6',2''-terpyridine)(2,6-pyridinedicarboxylate) 、 二甲基亚砜 反应 0.25h， 以43%的产率得到[Ru^II(κ²-pdc)(tpy)(DMSO)]
  参考文献：
  名称：

  Alkene Epoxidation Catalysts [Ru(pdc)(tpy)] and [Ru(pdc)(pybox)] Revisited: Revealing a Unique Ru^IV═O Structure from a Dimethyl Sulfoxide Coordinating Complex

  摘要：

  The X-ray crystal structure of a dimethyl sulfoxide (DMSO) coordinating complex [Ru-II(kappa(2)-pdc)(tpy)(DMSO)] (H(2)pdc = 2,6-pyridyl dicarboxylic acid and tpy = 2,2':6',2 ''-terpyridine) led to the discovery of a unique Ru-IV=O configuration for the Ru-pybox (pybox = pyridine-bis(oxazoline) ligands) epoxidation catalyst by theoretical calculations. On the basis of this structure, a detailed theoretical study was conducted on the alkene epoxidation reaction using ruthenium-based epoxidation catalysts. It was found that the process of H2O2 coordination proceeded via an associative path in which one carboxylate detached. The following H2O-elimination step was found to be facilitated by the detached carboxylate group. The resulting Ru-IV=O rearranges to the species trans-2a-oxo, in which one carboxylate group is situated over the tpy ring; the trans-2a-oxo was found to have the lowest activation free energies toward alkene epoxidation. These results demonstrated the importance of the hemilabile properties of the pdc(2-) ligand for the Ru-pdc alkene epoxidation catalysts.

  DOI：

  10.1021/acscatal.5b00496
• 作为产物：
  描述：

  吡啶-2,6-二甲酸 、 Ru(tpy)(Cl)₃ 在 Na₂CO₃ 作用下， 以 水 为溶剂， 以65%的产率得到Ru(2,2':6',2''-terpyridine)(2,6-pyridinedicarboxylate)
  参考文献：
  名称：

  Structures, electrochemical and spectroscopic properties of ternary ruthenium(II)-polypyridyl complexes with additional carboxylate, biguanide or sulfonamide donors

  摘要：

  The following complexes have been prepared: [Ru(bipy)(2)(pic)][PF6] (bipy = 2,2'-bipyridine; Hpic = picolinic acid); [Ru(terpy)(dipic)] (terpy =2,2':6',2"-terpyridine; H(2)dipic=dipicolinic acid); [Ru(bipy)(2) (Hbig)][PF6](2) (Hbig=biguanide); and [Ru(bipy)(2)(apps)][PF6] [where Happs is the p-tolylsulfonamide of 2-(2-aminophenyl)-pyridine]. The latter three have been characterised by X-ray crystallography and are all mononuclear pseudo-octachedral complexes. Electrochemical studies reveal the relationship between the potential of the metal-based Ru(II)/Ru(III) couple, with the potential values being clearly related to the sigma-donor or pi-acceptor capabilities of the ligands. The energies of the lowest-energy m.l.c.t. maxima in the electronic spectra also correlate with ligand properties. [Ru(bipy)(2)(Hbig)][PF6](2), which has a dissociable proton on the biguanide ligand, undergoes deprotonation in strongly basic conditions (pK(a) = 12.3 +/- 0.2), which results in a red-shift of the m.l.c.t. transition consistent with weakening of the ligand field due to the increased pi-donor capability of the deprotonated ligand. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(98)00145-4
• 作为试剂：
  描述：

  2-萘甲醚 在 Ru(2,2':6',2''-terpyridine)(2,6-pyridinedicarboxylate) 、 双氧水 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 7.0h， 以45%的产率得到2-甲氧基-1,4-萘醌
  参考文献：
  名称：

  选择性钌催化氧化萘和苯酚的新方法

  摘要：

  使用钌（2,2'，6'：2''-叔吡啶）（2,6-吡啶二羧酸盐）[Ru（tpy）（pydic）]为催化剂，过氧化氢为末端氧化剂，将芳烃选择性氧化为相应的醌。使用烷基化的萘和酚，苯并和萘醌的收率高达93％，工业上令人感兴趣的2-甲基萘的氧化反应产生了74％的相应醌和60％的甲萘醌（维生素K 3）2,3,5。 -构成维生素E关键中间体的三甲基苯醌的收率为83％。

  DOI：

  10.1002/adsc.201000137

文献信息

• A new A3B zinc(II)-porphyrin ligand and its ruthenium(II) complex: Synthesis, photophysical properties and photocatalytic applications
  作者：Xiu-yue Yu、Hui Su、Xin Zheng、Wen-bo Liu、Yao He、Na-na Fei、Ru Qiao、Yun-lai Ren、Cao-yuan Niu

  DOI：10.1016/j.molstruc.2021.130358

  日期：2021.8

  Porphyrins and metalloporphyrins (or porphyrin coordination complexes) have been wildly investigated as photocatalysts in recent years. Herein we synthesized two new A3B porphyrins, a new asymmetric A3B zinc-porphyrin ligand with peripheral chelate group (pyridine dicarboxylate), and a ruthenium(II) complex of the porphyrin ligand. Their photo-physical properties were characterized and investigated

  近年来，对卟啉和金属卟啉（或卟啉配位配合物）作为光催化剂进行了广泛的研究。在这里，我们合成了两个新的A 3 B卟啉，一个新的不对称A 3具有外围螯合基团（吡啶二羧酸盐）的B锌卟啉配体，以及卟啉配体的钌（II）配合物。通过紫外可见光谱和荧光发射对它们的光物理性质进行了表征和研究。通过DFT理论计算优化了分子结构的建模。所有卟啉化合物在Soret谱带和Q谱带均显示出强吸收性。就荧光而言，卟啉的游离碱比其他两种锌卟啉和钌-卟啉具有更高的量子产率和更长的寿命。此外，钌-卟啉配合物可用作可见光在两种有机反应中的光催化剂：
• Novel ruthenium–pyridinedicarboxylate complexes of terpyridine and chiral bis(oxazolinyl)pyridine: a new catalytic system for alkene epoxidation with [bis(acetoxy)iodo]benzene as an oxygen donor
  作者：Hisao Nishiyama、Yukihiro Motoyama

  DOI：10.1039/a705109c

  日期：——

  Ruthenium–pyridine-2,6-dicarboxylate (pydic) complexes 1–3 of terpyridine and chiral bis(oxazolinyl)pyridines (pybox-ip and pybox-ph), which can be synthesized from [Ru(p-cymene)Cl2]2 and the corresponding ligands, exhibit catalytic activity for epoxidation of trans-stilbene in combination with [bis(acetoxy)iodo]benzene: asymmetric induction with 2 was observed in 74% ee for trans-stilbene.

  三联吡啶和手性双(恶唑啉基)吡啶 (pybox-ip 和 pybox-ph) 的钌钌-吡啶-2,6-二羧酸盐 (pydic) 络合物 1-3，可以由 [Ru(p-伞花烃)Cl2 合成]2 和相应的配体，对反式二苯乙烯与[双（乙酰氧基）碘]苯结合的环氧化表现出催化活性：在反式二苯乙烯的 74% ee 中观察到与 2 的不对称诱导。
• Structures, electrochemical and spectroscopic properties of ternary ruthenium(II)-polypyridyl complexes with additional carboxylate, biguanide or sulfonamide donors
  作者：Samantha M Couchman、José M Dominguez-Vera、John C Jeffery、Colin A McKee、Simon Nevitt、Matthias Pohlman、Claire M White、Michael D Ward

  DOI：10.1016/s0277-5387(98)00145-4

  日期：1998.9

  The following complexes have been prepared: [Ru(bipy)(2)(pic)][PF6] (bipy = 2,2'-bipyridine; Hpic = picolinic acid); [Ru(terpy)(dipic)] (terpy =2,2':6',2"-terpyridine; H(2)dipic=dipicolinic acid); [Ru(bipy)(2) (Hbig)][PF6](2) (Hbig=biguanide); and [Ru(bipy)(2)(apps)][PF6] [where Happs is the p-tolylsulfonamide of 2-(2-aminophenyl)-pyridine]. The latter three have been characterised by X-ray crystallography and are all mononuclear pseudo-octachedral complexes. Electrochemical studies reveal the relationship between the potential of the metal-based Ru(II)/Ru(III) couple, with the potential values being clearly related to the sigma-donor or pi-acceptor capabilities of the ligands. The energies of the lowest-energy m.l.c.t. maxima in the electronic spectra also correlate with ligand properties. [Ru(bipy)(2)(Hbig)][PF6](2), which has a dissociable proton on the biguanide ligand, undergoes deprotonation in strongly basic conditions (pK(a) = 12.3 +/- 0.2), which results in a red-shift of the m.l.c.t. transition consistent with weakening of the ligand field due to the increased pi-donor capability of the deprotonated ligand. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Alkene Epoxidation Catalysts [Ru(pdc)(tpy)] and [Ru(pdc)(pybox)] Revisited: Revealing a Unique Ru^IV═O Structure from a Dimethyl Sulfoxide Coordinating Complex
  作者：Ying Wang、Lele Duan、Lei Wang、Hong Chen、Junliang Sun、Licheng Sun、Mårten S. G. Ahlquist

  DOI：10.1021/acscatal.5b00496

  日期：2015.7.2

  The X-ray crystal structure of a dimethyl sulfoxide (DMSO) coordinating complex [Ru-II(kappa(2)-pdc)(tpy)(DMSO)] (H(2)pdc = 2,6-pyridyl dicarboxylic acid and tpy = 2,2':6',2 ''-terpyridine) led to the discovery of a unique Ru-IV=O configuration for the Ru-pybox (pybox = pyridine-bis(oxazoline) ligands) epoxidation catalyst by theoretical calculations. On the basis of this structure, a detailed theoretical study was conducted on the alkene epoxidation reaction using ruthenium-based epoxidation catalysts. It was found that the process of H2O2 coordination proceeded via an associative path in which one carboxylate detached. The following H2O-elimination step was found to be facilitated by the detached carboxylate group. The resulting Ru-IV=O rearranges to the species trans-2a-oxo, in which one carboxylate group is situated over the tpy ring; the trans-2a-oxo was found to have the lowest activation free energies toward alkene epoxidation. These results demonstrated the importance of the hemilabile properties of the pdc(2-) ligand for the Ru-pdc alkene epoxidation catalysts.