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| 2. |
- Belyaev, A. N., et al.
(författare)
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Redox properties of rhodium(III) oxo-bridged carboxylate complexes
- 2001
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Ingår i: Russian journal of general chemistry. - 1070-3632 .- 1608-3350. ; 71:8, s. 1186-1193
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Tidskriftsartikel (refereegranskat)abstract
- Chemical and electrochemical oxidation of rhodium (III) oxo-bridged carboxylate complexes was studied. The chemical [with O-3 and Ce(IV) salts] or electrochemical (at potentials of 1.00-1.20 V) oxidations of the binuclear complexes [Rh-2(mu-O)(mu-O2CCH3)(2)(H2O)(6)](2+) and [Rh-2(mu-O)(mu-O2CCF3)(2)(H2O)(6)](2+) leads to the superoxo complexes [Rh-2(mu-O)(O-2(-))(mu-O2CCH3)(2)(H2O)(5)]+ and [Rh-2(mu-O)(O-2(-))(mu-O2CCF3)(2)(H2O)(5)](+) with terminal coordination of O-2(-). The trinuclcar acetate [Rh-3(mu(3)-O)(mu-O2CCH3)(6)(H2O)(3)](+), unlike its trifluoroacetate analog [Rh-3(mu(3)-O)(mu-O2CCF3)(6)(H2O)(3)](+), is oxidized only electrochemically at a potential of 1.38 V. The oxidation of [Rh-3(mu(3)-O)(mu-O2CCH3)(6)(H2O)(3)](+) is reversible and involves formation of an unstable superoxo group O-2(-) between two Rh-3(III)(mu(3)-O) cores.
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| 6. |
- Duan, Lele, et al.
(författare)
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Chemical and Photochemical Water Oxidation Catalyzed by Mononuclear Ruthenium Complexes with a Negatively Charged Tridentate Ligand
- 2010
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 16:15, s. 4659-4668
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Tidskriftsartikel (refereegranskat)abstract
- Two mononuclear ruthenium complexes [RuL(pic)(3)] (1) and [RuL(bpy)(pic)] (2) (H2L = 2,6-pyridinedicarboxylic acid, pic=4-picoline, bpy = 2,2'-bipyridine) have been synthesized and fully characterized. Both complexes could promote water oxidation chemically and photochemically. Compared with other known ruthenium-based water oxidation catalysts using [Ce(NH4)(2)(NO3)(6)] (Ce-IV) as the oxidant in solution at pH 1.0, complex 1 is one of the most active catalysts yet reported with an initial rate of 0.23 turnovers(-1). Under acidic conditions, the equatorial 4-picoline in complex 1 dissociates first. In addition, ligand exchange in 1 occurs when the Rum state is reached. Based on the above observations and MS measurements of the intermediates during water oxidation by 1 using Ce-IV as oxidant, [RuL(pic)(2)(H2O)](+) is proposed as the real water oxidation catalyst.
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| 7. |
- Eremina, A. V., et al.
(författare)
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Ruthenium(II,III,III) mu(3)-oxotrifluoroacetate with dimethyl sulfoxide : Synthesis, structure, and DTF quantum-chemical calculations
- 2007
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Ingår i: Russian journal of coordination chemistry. - 1070-3284 .- 1608-3318. ; 33:9, s. 669-673
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Tidskriftsartikel (refereegranskat)abstract
- The reaction of [Ru-3(III) (mu(3)-O)(mu-O2CCF3)(6)(H2O)(3)](O2CCF3) in methanol gives two solvates, [Ru3O(O2CCF3)(6)(DMSO)(3)] center dot 1/2H(2)O (I) and [Ru3O(O2CCF3)(6)(DMSO)(3)] center dot H2O (II), of a novel trinuclear mixedvalence Ru(II,III,III) trifluoroacetate complex, where two DMSO molecules are coordinated to the Ru atoms through the O atom, while the third DMSO molecule is coordinated through the S atom. According to the X-ray diffraction data, the complex can crystallize in two crystal systems: triclinic (I) (space group P (1) over bar) and monoclinic (II) (space group P2(1)/m). The unit cell parameters for I are: a = 9.354, b = 11.005, c = 20.846 angstrom, alpha = 99.10, beta = 96.38, gamma = 92.17, Z = 2; R = 7.27%; for I are: a = 9.186, b = 17.044, c = 13.091 angstrom, beta = 101.10, Z = 2; R = 14.18%.
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| 8. |
- Fischer, Andreas, et al.
(författare)
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Crystal formation involving 1-methylbenzimidazole in iodide/triiodide electrolytes for dye-sensitized solar cells
- 2007
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Ingår i: Solar Energy Materials and Solar Cells. - : Elsevier BV. - 0927-0248 .- 1879-3398. ; 91:12, s. 1062-1065
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Tidskriftsartikel (refereegranskat)abstract
- Nitrogen heterocyclic compounds, such as N-methylbenzimidazole (MBI), are commonly used as additives to electrolytes for dye-sensitized solar cells (DSCs), but the chemical transformation of additives in electrolyte solutions remains poorly understood. Solid crystalline compound (MBI)(6)(MBI-H+)(2)(I-)(I-3(-)) (1) was isolated from different electrolytes for DSCs containing MBI as additive. The crystal structure of I was determined by single-crystal X-ray diffraction. In the crystal structure, 1 contains neutral and protonated MBI fragments; iodide and triiodide anions form infinite chains along the crystallographic a-axis. The role of the solvent and additives in the crystallization process in electrolytes is discussed.
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| 9. |
- Fischer, A. I., et al.
(författare)
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Synthesis, crystal and molecular structures of the octanuclear cationic mixed-valence cobalt acetate complex
- 2007
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Ingår i: Russian journal of coordination chemistry. - 1070-3284 .- 1608-3318. ; 33:11, s. 789-794
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Tidskriftsartikel (refereegranskat)abstract
- A new octanuclear mixed-valence cobalt acetate complex of the cationic type [Co-4(II) Co4(III) (mu(4)-O)(4)(mu(3)-OMe)(4)(mu-OAc)(6)(H2O)(8)]F-2 center dot 10H(2)O ([I]F-2 center dot 10H(2)O) was prepared by crystallization from a solution of 'cobalt(III) acetate' in a Me2CO-MeOH-H2O-HF mixture and studied by X-ray diffraction. The crystals are monoclinic: space group C2/c, a = 17.222 angstrom, b = 16.836 angstrom, c = 16.586 angstrom, beta = 94.902 degrees, Z = 4, R = 4.37% (I > 2 sigma(I)). In the crystal, the I2+ complex cations, fluoride anions, and solvate water molecules form a three-dimensional (3D) coordination supermolecular system.
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| 10. |
- Gorlov, Mikhail, et al.
(författare)
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Arene complexes of gallium : An effective tool for the synthesis of transition metal clusters and complexes
- 2008
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Ingår i: Coordination chemistry reviews. - : Elsevier BV. - 0010-8545 .- 1873-3840. ; 252:15-17, s. 1564-1576
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Tidskriftsartikel (refereegranskat)abstract
- In this review, the interactions between gallium(III) halides or gallium(I) subvalent halides and aromatic hydrocarbons in solution and solid state are discussed. Such unique properties of gallium halides-arene mixtures as the ability to reduce metallic centers and accept halide atoms make them very efficient tool for the preparation of low-valent clusters and complexes of transition metals. Diverse mono- and polynuclear arene complexes of d- and f-elements, including coordination polymers, may be achieved by the reactions between transition metal halides and gallium(III) halides in arene media. The role of Lewis acidity of gallium halides, the nature of the substituents on the arene ring and the nature of transition metals are discussed in terms of coordination mode of arenes and resulting structure of the transition metal-arene complexes.
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