[Ru(II)2(μ-2,3,5,6-tetrakis(2-pyridyl)pyrazine-N,N',N'')(2,2':6'2''-terpyridine)(methyl-3,5-di(2-pyridyl)benzoate(-H))](3+) | 1190920-15-0

• 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: [Ru(II)2(μ-2,3,5,6-tetrakis(2-pyridyl)pyrazine-N,N',N'')(2,2':6'2''-terpyridine)(methyl-3,5-di(2-pyridyl)benzoate(-H))](3+)
• 英文别名: [Ru2(μ-tppz)(tpy)(MeOCOC6H2(C5H4N)2)](3+)
• CAS: 1190920-15-0
• 化学式: C₅₇H₄₀N₁₁O₂Ru₂
• 分子量: 1113.16
• InChiKey: MWVIZSDBRPNDHY-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  [Ru(II)2(μ-2,3,5,6-tetrakis(2-pyridyl)pyrazine-N,N',N'')(2,2':6'2''-terpyridine)(methyl-3,5-di(2-pyridyl)benzoate(-H))](3+) 在 (NH₄)2[Ce(NO₃)6] 作用下， 以 乙腈 为溶剂， 生成 [Ru(II)Ru(III)(μ-2,3,5,6-tetrakis(2-pyridyl)pyrazine)(2,2':6'2''-terpyridine)(methyl-3,5-di(2-pyridyl)benzoate(-H))](4+)
  参考文献：
  名称：

  Redox Chemistry and Electronic Properties of 2,3,5,6-Tetrakis(2-pyridyl)pyrazine-Bridged Diruthenium Complexes Controlled by N,C,N′-BisCyclometalated Ligands

  摘要：

  To investigate the consequences of cyclometalation for electronic communication in dinuclear ruthenium complexes, a series of 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) bridged diruthenium complexes was prepared and studied. These complexes have a central tppz ligand bridging via nitrogen-to-ruthenium coordination bonds, while each ruthenium atom also binds either a monoanionic, N,C,N'-terdentate 2,6-bis(2'-pyridyl)phenyl (R-N boolean AND C boolean AND N) ligand or a 2,2':6',2 ''-terpyridine (tpy) ligand. The N,C,N'-, that is, biscyclometalation, instead of the latter N,N', N ''-bonding motif significantly changes the electronic properties of the resulting complexes. Starting from well-known [{Ru(tpy)}(2)(mu-tppz)](4+) (tpy = 2,2':2 '',6-terpyridine) ([3](4+)) as a model compound, the complexes [{Ru(R-N boolean AND C boolean AND N)}(mu-tppz){Ru(tpy)}](3+) (R-N boolean AND C(H)boolean AND N = 4-R-1,3-dipyridylbenzene, R = H ([4a](3+)), CO2Me ([4b](3+))), and [{Ru(R-N boolean AND C boolean AND N)}(2)(mu-tppz)](2+), (R = H ([5a](2+)), CO2Me ([5b](2+))) were prepared with one or two N,C,N'-cyclometalated terminal ligands. The oxidation and reduction potentials of cyclometalated [4](3+) and [5](2+) are shifted negatively compared to non-cyclometalated [3](4+), the oxidation processes being affected more significantly. Compared to [3](4+), the electronic spectra of [5](2+) display large bathochromic shifts of the main MLCT transitions in the visible spectral region with low-energy absorptions tailing down to the NIR region. One-electron oxidation of [3](4+) and [5](2+) gives rise to low-energy absorption bands. The comproportionation constants and NIR band shape correspond to delocalized Robin-Day class III compounds. Complexes [4a](3+) (R = H) and [4b](3+) (R = CO2Me) also exhibit strong electronic communication, and notwithstanding the large redox-asymmetry the visible metal-to-ligand charge-transfer absorption is assigned to originate from both metal centers. The potential of the first, ruthenium-based, reversible oxidation process is strongly negatively shifted. On the contrary, the second oxidation is irreversible and cyclometalated ligand-based. Upon one-electron oxidation, a weak and low-energy absorption arises.

  DOI：

  10.1021/ic801897k
• 作为产物：
  描述：

  [Ru(II)Ru(III)(μ-2,3,5,6-tetrakis(2-pyridyl)pyrazine)(2,2':6'2''-terpyridine)(methyl-3,5-di(2-pyridyl)benzoate(-H))](4+) 在 Fe(C₅H₅)2 作用下， 以 乙腈 为溶剂， 生成 [Ru(II)2(μ-2,3,5,6-tetrakis(2-pyridyl)pyrazine-N,N',N'')(2,2':6'2''-terpyridine)(methyl-3,5-di(2-pyridyl)benzoate(-H))](3+)
  参考文献：
  名称：

  Redox Chemistry and Electronic Properties of 2,3,5,6-Tetrakis(2-pyridyl)pyrazine-Bridged Diruthenium Complexes Controlled by N,C,N′-BisCyclometalated Ligands

  摘要：

  To investigate the consequences of cyclometalation for electronic communication in dinuclear ruthenium complexes, a series of 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) bridged diruthenium complexes was prepared and studied. These complexes have a central tppz ligand bridging via nitrogen-to-ruthenium coordination bonds, while each ruthenium atom also binds either a monoanionic, N,C,N'-terdentate 2,6-bis(2'-pyridyl)phenyl (R-N boolean AND C boolean AND N) ligand or a 2,2':6',2 ''-terpyridine (tpy) ligand. The N,C,N'-, that is, biscyclometalation, instead of the latter N,N', N ''-bonding motif significantly changes the electronic properties of the resulting complexes. Starting from well-known [{Ru(tpy)}(2)(mu-tppz)](4+) (tpy = 2,2':2 '',6-terpyridine) ([3](4+)) as a model compound, the complexes [{Ru(R-N boolean AND C boolean AND N)}(mu-tppz){Ru(tpy)}](3+) (R-N boolean AND C(H)boolean AND N = 4-R-1,3-dipyridylbenzene, R = H ([4a](3+)), CO2Me ([4b](3+))), and [{Ru(R-N boolean AND C boolean AND N)}(2)(mu-tppz)](2+), (R = H ([5a](2+)), CO2Me ([5b](2+))) were prepared with one or two N,C,N'-cyclometalated terminal ligands. The oxidation and reduction potentials of cyclometalated [4](3+) and [5](2+) are shifted negatively compared to non-cyclometalated [3](4+), the oxidation processes being affected more significantly. Compared to [3](4+), the electronic spectra of [5](2+) display large bathochromic shifts of the main MLCT transitions in the visible spectral region with low-energy absorptions tailing down to the NIR region. One-electron oxidation of [3](4+) and [5](2+) gives rise to low-energy absorption bands. The comproportionation constants and NIR band shape correspond to delocalized Robin-Day class III compounds. Complexes [4a](3+) (R = H) and [4b](3+) (R = CO2Me) also exhibit strong electronic communication, and notwithstanding the large redox-asymmetry the visible metal-to-ligand charge-transfer absorption is assigned to originate from both metal centers. The potential of the first, ruthenium-based, reversible oxidation process is strongly negatively shifted. On the contrary, the second oxidation is irreversible and cyclometalated ligand-based. Upon one-electron oxidation, a weak and low-energy absorption arises.

  DOI：

  10.1021/ic801897k