Ground- and Excited-State Properties of Ruthenium(II) Complexes Containing Tridentate Azine Ligands, Ru(tpy)(bpy)L2+, Where L Is a Polymerizable Acetylene

Rasmussen, Seth C.; Ronco, Silvia; Mlsna, Debra A.; Billadeau, Mark A.; Pennington, William T.; Kolis, Joseph W.; Petersen, John D.

doi:10.1021/ic00108a013

Cited by 91 publications

(70 citation statements)

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“…[12] The C(33)ϪC(34) [Ru(bpy)(tpy)(ppa)](PF 6 ) 2 ·acetone (1.187 Å ) (pa ϭ pyridylacetylene, and ppa ϭ phenylpyridylacetylene). [18] Of the three phenylene groups, the outer two are coplanar because of the inversion center. The dihedral angle with the central phenylene group is 65°.…”

Section: Resultsmentioning

confidence: 99%

X-ray Structure of a Ruthenium Dinuclear Complex Incorporating 4,4′-Bis(cyanamidophenylethynyl)benzene as a Ligand, a Conjugated Bridge Two Nanometers in Length

Sondaz¹,

Jaud²,

Launay³

et al. 2002

Eur. J. Inorg. Chem.

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Keywords: Ruthenium / Bridging ligands / N ligands / X-ray structureThe reaction of [Ru(bpy)(tpy)(Ipcyd)] + (bpy = 2,2Ј-bipyridine, tpy = 2,2Ј:6Ј,2ЈЈ-terpyridine, Ipcyd = 4-iodophenylcyanamide anion) with diethynylbenzene in a Sonogashira cross-coupling reaction gives an unprecedentedly long and conjugated dinuclear complex [{[Ru(bpy)(tpy)] 2 (µ-dcpeb)}(BPh 4 ) 2 ]· 4(PhCH 3 ) (dcpeb = dicyanamidophenylethynylbenzene dianion). The crystal structure data are as follows: crystal sys-

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Section: Resultsmentioning

confidence: 99%

X-ray Structure of a Ruthenium Dinuclear Complex Incorporating 4,4′-Bis(cyanamidophenylethynyl)benzene as a Ligand, a Conjugated Bridge Two Nanometers in Length

Sondaz¹,

Jaud²,

Launay³

et al. 2002

Eur. J. Inorg. Chem.

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“…The behavior found is in good agreement with previous work. 37,64 The second and third reduction waves were observed as irreversible waves at lower scan rates. Analysis of peak currents for the second reduction indicates that at sweep rates below 0.1 V/s, the anodic peak current becomes much less than its cathodic predecessor.…”

Section: ■ Experimental Sectionmentioning

confidence: 97%

Thermodynamic and Kinetic Hydricity of Ruthenium(II) Hydride Complexes

et al. 2012

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Despite the fundamental importance of the hydricity of a transition metal hydride (ΔG(H–)°(MH) for the reaction M–H → M+ + H–) in a range of reactions important in catalysis and solar energy storage, ours (J. Am. Chem. Soc.2009, 131, 2794) are the only values reported for water solvent, and there has been no basis for comparison of these with the wider range already determined for acetonitrile solvent, in particular. Accordingly, we have used a variety of approaches to determine hydricity values in acetonitrile of Ru(II) hydride complexes previously studied in water. For [Ru(η(6)-C6Me6)(bpy)H]+ (bpy = 2,2′-bipyridine), we used a thermodynamic cycle based on evaluation of the acidity of [Ru(η(6)-C6Me6)(bpy)H]+ pKa = 22.5 ± 0.1 and the [Ru(η(6)-C6Me6)(bpy)(NCCH3)(1/0)](2+/0) electrochemical potential (−1.22 V vs Fc+/Fc). For [Ru(tpy)(bpy)H]+ (tpy = 2,2′:6′,2″-terpyridine) we utilized organic hydride ion acceptors (A+) of characterized hydricity derived from imidazolium cations and pyridinium cations, and determined K for the hydride transfer reaction, S + MH+ + A+ → M(S)2+ + AH (S = CD3CN, MH+ = [Ru(tpy)(bpy)H]+), by 1H NMR measurements. Equilibration of initially 7 mM solutions was slow--on the time scale of a day or more. When E°(H+/H–) is taken as 79.6 kcal/mol vs Fc+/Fc as a reference, the hydricities of [Ru(η(6)-C6Me6)(bpy)H]+ and [Ru(tpy)(bpy)H]+ were estimated as 54 ± 2 and 39 ± 3 kcal/mol, respectively, in acetonitrile to be compared with the values 31 and 22 kcal/mol, respectively, found for aqueous media. The pKa estimated for [Ru(tpy)(bpy)H]+ in acetonitrile is 32 ± 3. UV–vis spectroscopic studies of [Ru(η(6)-C6Me6)(bpy)]0 and [Ru(tpy)(bpy)]0 indicate that they contain reduced bpy and tpy ligands, respectively. These conclusions are supported by DFT electronic structure results. Comparison of the hydricity values for acetonitrile and water reveals a flattening or compression of the hydricity range upon transferring the hydride complexes to water.

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“…The trans axial positions are occupied by the N3 (azo) atom of azpy and the Br atom. The bite angle of azpy ligand (76.17 (13) However, these are longer than those observed in the bpy complexes, for example, [Ru(tpy)(bpy)(I)](PF6)20.5C7H8 (2.019 Å), 7 [Ru(tpy)(bpy)(pz)](PF6)2 (2.013 Å), 8 [Ru(tpy)(bpy)-(CH3CN)](PF6)2 (2.031 Å), 9 and [Ru(tpy)(bpz)(Cl)](PF6)2·CH3CN (2.037 Å). 10 This phenomenon can be ascribed to the π-interaction between metal ion and ligands.…”

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confidence: 86%

Crystal Structure of Bromo(2,2′:6′,2″-terpyridine)(2-(phenylazo)- pyridine)ruthenium(II) Tetrafluoroborate

et al. 2003

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The polypyridine complexes of a type [Ru(tpy)(L)X] n+ (where tpy = 2,2′:6′,2″-terpyridine, L = a bidentate ligand such as 2,2′-bipyridine (bpy), X = a monodentate ligand and n = 0 or 1) have generated considerable interest in several areas, for example, used as effective DNA cleavage agents 1 and as catalysts in oxidation of water to dioxygen 2 based on the corresponding high-valent ruthenium oxo complexes. It is our continuing interest to study structures of ruthenium(II) complexes with a bidentate ligand such as 2-(phenylazo)pyridine (azpy) according to its property as a strong π-acceptor. 3 Azpy and [Ru(tpy)Cl3] were synthesized by procedures reported in the literatures, 3,4 [Ru(tpy)(azpy)Cl]Cl was prepared using a similar method to that described before. 5[Ru(tpy)(azpy)Cl]Cl (52 mg) and AgNO3 (30 mg) were refluxed in the mixture of acetone and water for 1 h and the solution was filtered while hot. LiBr (42 mg) was added to the filtrate, and the mixture was heated and refluxed for 1 h. NH4BF4 (45 mg) was added to the solution. After 5 days, the solid was collected and crystals suitable for X-ray techniques were selected from the obtained solid. Details of the X-ray structure determination of the title compound are given in Tables 1 -3. The ruthenium center is in a distorted octahedral environment with three nitrogens (N4, N5, N6) of the tpy ligand and the N1 (py) atom of azpy ligand in the equatorial plane. The trans axial positions are occupied by the N3 (azo) atom of azpy and the Br atom. The bite angle of azpy ligand (76.17 (13) This phenomenon can be ascribed to the π-interaction between metal ion and ligands. Since azpy is a stronger π-acceptor than bpy and bpz, the ruthenium ion becomes an electron-rich center and lengthens the distances to tpy ligand in order to stabilize the structure of complex ion. The Ru-Br bond length in the title compound (2.547(5)Å) is slightly longer than those observed in [Ru(C5H5)(CO)2Br] (2.536(2)Å) 11 but shorter than those in [Ru(Br)2(Me2SO)4] (2.601(1), 2.578(1)Å). 12 The Ru-N(azo) distance (1.960(3)Å) is shorter than the Ru-N(py) distance (2.061(3)Å) and becomes shortest among the related complexes. 2,5,6 This indicates that there is strong π-backbonding in the title compound, greater The title compound, C26H20N6BrRu(BF4), crystallizes in the centrosymmetric space group P21/n and consists of discrete complex units. The Ru(II) ion is octahedrally coordinated to one 2,2′:6′,2″-terpyridine (tpy), one 2-(phenylazo)pyridine (azpy) and a Br atom in trans-axial position at a distance of 2.547(5)Å. The shorter Ru-N (azo) distance (1.960(3)Å) than the Ru-N(py) distance (2.061(3)Å) signifies a strong π-backbonding, which leads to a longer, N=N (azo) bond (1.304(4)Å). † To whom correspondence should be addressed. E-mail: thlu@phys.nthu.edu.tw than in other complexes, and that bromide has a weaker π-bond interaction with the metal ion compared to chloride, acetonitrile and the nitro group. In addition, the N=N bond distance (1.304(4)Å), which is sensitive to the extent of π-backbo...

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Ground- and Excited-State Properties of Ruthenium(II) Complexes Containing Tridentate Azine Ligands, Ru(tpy)(bpy)L2+, Where L Is a Polymerizable Acetylene

Cited by 91 publications

References 5 publications

X-ray Structure of a Ruthenium Dinuclear Complex Incorporating 4,4′-Bis(cyanamidophenylethynyl)benzene as a Ligand, a Conjugated Bridge Two Nanometers in Length

X-ray Structure of a Ruthenium Dinuclear Complex Incorporating 4,4′-Bis(cyanamidophenylethynyl)benzene as a Ligand, a Conjugated Bridge Two Nanometers in Length

Thermodynamic and Kinetic Hydricity of Ruthenium(II) Hydride Complexes

Crystal Structure of Bromo(2,2′:6′,2″-terpyridine)(2-(phenylazo)- pyridine)ruthenium(II) Tetrafluoroborate

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