Kinetics of the oxidation of hexaaquoiron(2+) by polypyridine complexes of ruthenium(III).  Negative enthalpies of activation

Braddock, James N.; Meyer, Thomas J.

doi:10.1021/ja00791a014

Cited by 167 publications

(79 citation statements)

References 5 publications

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“…The Ru complexes were prepared according to [62]. [Ru(phen),(CN)J [63] were prepared coulometrically using a Hg working electrode, a Pt wire as auxiliary electrode, and a SCE as reference.…”

Section: Experimental Partmentioning

confidence: 99%

Photogeneration of Carbon Monoxide and of Hydrogen via Simultaneous Photochemical Reduction of Carbon Dioxide and Water by Visible‐Light Irradiation of Organic Solutions Containing Tris(2,2′‐bipyridine)ruthenium(II) and Cobalt(II) Species as Homogeneous Catalysts

Ziessel¹,

Hawecker²,

Lehn³

1986

Helvetica Chimica Acta

147

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CO and H, are photogenerated simultaneously by visible-light irradiation of systems containing a photosensitizer, the [R~(bpy)~],+ complex, C o ( f f ) species as homogeneous catalysts, which mediate COz and H,O reduction by intermediate formation of Co(l), a tertiary amine as electron donor, which provides the electrons for the reduction, and an organic solvent which also facilitates dissolution of CO,. The efficiency of (CO + H,) gas production and the selectivity CO/H, markedly depend upon the composition of the medium, the nature of the tertiary amine, the solvent, and the ligand of the Co ions. 2,9-Dimethyl-l, 10-phenanthroline is particularly effective in promoting CO and H, formation, giving a quantum yield of 7.7% in (CO + H2) (1.2% for CO and 6.5% for H,). The process consists of two catalytic cycles: a photocatalytic cycle for the Ru complex and a double dark reaction pathway for the Co species; oxidative and/or reductive quenching of the excited state of the photosensitizer lead to the formation of Co (1) Over the last years, we have described three homogeneous catalytic systems which perform photochemical CO, reduction [7]: the first allows the simultaneous reduction of CO, and H,O into CO and H,, respectively, based on [Ru(bpy),]CI, (bpy = 2,2'-bipyridine) as photosensitizer and Co(1l) ions or Co(1I) complexes as catalyst [8], the second is highly efficient and selective for the reduction of CO, into CO and based on a single complex,fuc-[Re(bpy)(CO),]X (X = C1, Br) acting both as photosensitizer and as catalyst [9], and the third, based on Ru complexes, performs the photochemical reduction of CO, to formate [lo]. In our initial reports [8] [9], we described the simultaneous photo-

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Section: Experimental Partmentioning

confidence: 99%

Photogeneration of Carbon Monoxide and of Hydrogen via Simultaneous Photochemical Reduction of Carbon Dioxide and Water by Visible‐Light Irradiation of Organic Solutions Containing Tris(2,2′‐bipyridine)ruthenium(II) and Cobalt(II) Species as Homogeneous Catalysts

Ziessel¹,

Hawecker²,

Lehn³

1986

Helvetica Chimica Acta

147

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“…The products resulting from the quenching reaction can be identified from Figure 3. A spectrum with a maximum at 680 nm which is characteristic [9] of Ru(bipy)z+ can be observed 4 ps after laser excitation. The kinetic details are given in the inserted oscillograms which show the time course of the events at 680 nm.…”

mentioning

confidence: 95%

Ruthenium Dioxide Electrodes as Suitable Anodes for Water Photolysis

Neumann‐Spallart

Kalyanasundaram

Grätzel

et al. 1980

Helvetica Chimica Acta

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SummaryThis paper presents a cell system in which a photoinduced redox reaction occurs in the cathodic compartment which is coupled to a Ru02-anode. The light induced oxidation of the ruthenium complex Ru (bipy)$+ by peroxodisulfate is used to illustrate that even under diffuse room light irradiation the photopotentials developed at the Pt-cathode are sufficient to afford water oxidation in the anode compartment. The oxygen produced at the Ru02-electrode stands in a stochiometric relation to the current passed through the circuit. Implications for a cell system in which H2 and O2 are produced in separate compartments under illumination are discussed.Introduction. -The photochemical production of hydrogen from water is of primary interest in the field of solar energy conversion. A viable approach to the solution of this problem is the combination of a photo-redox process

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“…The emission of the ruthenium complex may arise from the energetic electron transfer reaction between Ru(phen) 3 3+ and a reducing agent. Ru(phen) 3 2+ is commercially available but it can be synthesized easily from ruthenium chloride and the common laboratory reagent 1,10-phenanthroline (16). Most ruthenium(II) complexes are expensive reagents.…”

Section: +mentioning

confidence: 99%

“…Ammonium peroxodisulphate was purchased from Kanto Chemical Co. (Tokyo, Japan). Tris(1,10-phenanthroline) ruthenium(II) bromide was prepared employing methods available in the literature (16). Chlorpheniramine (CPA) was a gift from the national pharmaceutical company (Oman, Muscat).…”

Section: Reagentsmentioning

confidence: 99%

Chemiluminescence determination of chlorpheniramine using tris(1,10‐phenanthroline)–ruthenium(II) peroxydisulphate system and sequential injection analysis

et al. 2008

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] and a peristaltic pump to propel the sample. The experimental conditions affecting the chemiluminescence reaction were systematically optimized, using the univariate approach. Under the optimum conditions linear calibration curves of 0.1-10 mg/ml were obtained. The detection limit was 0.04 mg/ml and the relative standard deviation (RSD) was always < 5%. The procedure was applied to the analysis of CPA in pharmaceutical products and was found to be free from interferences from concomitants usually present in these preparations.

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Kinetics of the oxidation of hexaaquoiron(2+) by polypyridine complexes of ruthenium(III). Negative enthalpies of activation

Abstract: Rate constants and activation parameters have been measured for the reactions between Fe(H20)62+ and the ruthenium(II1) complexes Ru(terpy)za+, R~( p h e n )~~+ , R~(bipy),~+, and R~(bipy),(py),~+. The net reac-

Cited by 167 publications

References 5 publications

Photogeneration of Carbon Monoxide and of Hydrogen via Simultaneous Photochemical Reduction of Carbon Dioxide and Water by Visible‐Light Irradiation of Organic Solutions Containing Tris(2,2′‐bipyridine)ruthenium(II) and Cobalt(II) Species as Homogeneous Catalysts

Photogeneration of Carbon Monoxide and of Hydrogen via Simultaneous Photochemical Reduction of Carbon Dioxide and Water by Visible‐Light Irradiation of Organic Solutions Containing Tris(2,2′‐bipyridine)ruthenium(II) and Cobalt(II) Species as Homogeneous Catalysts

Ruthenium Dioxide Electrodes as Suitable Anodes for Water Photolysis

Chemiluminescence determination of chlorpheniramine using tris(1,10‐phenanthroline)–ruthenium(II) peroxydisulphate system and sequential injection analysis

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