18955-01-6Relevant academic research and scientific papers
Understanding the facile photooxidation of Ru(bpy)32+ in strongly acidic aqueous solution containing dissolved oxygen
Das, Amitava,Joshi, Vishwas,Kotkar, Dilip,Pathak, Vinit S.,Swayambunathan,Kamat, Prashant V.,Ghosh, Pushpito K.
, p. 6945 - 6954 (2007/10/03)
The facile photooxidation of Ru(bpy)32+ to Ru(bpy)33+ in oxygenated solutions of H2SO4 was presented. Chromatographic, spectroscopic, electrochemical and optical rotation studies revealed t
Decrease in the Oxidation Potential of the Tris-2,2'-bipyridyl Ruthenium(II) Complex Upon Electrostatic Binding to Colloidal Silica as Evidenced on the Basis of the Reaction with the Azidyl Radical
Naik, Devidas B.,Schnabel, Wolfram
, p. 1559 - 1562 (2007/10/02)
The azidyl radical which is otherwise unreactive towards the Ru(bpy)32+ complex reacts with this complex in aqueous solution provided negatively charged colloidal silica particles are present.The increase in reactivity is explained in terms of ion binding, i.e.Ru(bpy)32+ complexes becoming rather firmly attached to the negatively charged particles.The attachment causes a decrease in the redox potential of the system Ru(bpy)33+/Ru(bpy)32+ from E0 = 1.27 V vs.NHE (in the absence of colloidal silica) to E0 = 1.17 V vs.NHE (in the presence of colloidal silica).This value was obtained on the basis of E0 = 1.35 V vs.NHE for the system .N3/N3-. - Keywords: Colloides / Complex Compounds /Radiation Chemistry / Radicals
Kinetics and Products of the Reactions of NO3 with Monoalkenes, Dialkenes, and Monoterpenes
DeFelippis, Michael R.,Faraggi, M.,Klapper, Michael H.
, p. 2420 - 2424 (2007/10/02)
Rate constants for the reactions of NO3 with a number of aliphatic mono- and dialkenes and monoterpenes have been determined in a 420 l reaction chamber at 1-bar total pressure of synthetic air by 298 K with a relative kinetic method.The products of these reactions have been investigated also at 1-bar total pressure of synthetic air with in situ FT-IR spectrometry and gas chromatography.In all cases, the initial formation of thermally unstable nitrooxy-peroxynitrate-type compounds containing the difunctional group -CH(OONO2)-CH(ONO2)- has been observed.The experimental results are consistent with a mechanism involving the formation of nitrooxy-alkoxy radicals, -CH(O)-CH(ONO2)-, via the self-reaction of the nitrooxy-peroxy radicals.The further reactions of the nitrooxy-alkoxy radicals then determine the final products.The main reaction pathways are (i) reaction with O2 to form nitrooxy-aldehydes or -ketones and HO2 and (II) thermal decomposition forming aldehydes/ketones and NO2.The mechanisms leading to the final products are discussed, and their possible relevance for the chemistry in the troposphere is considered.
Photoinduced electron transfer with [Fe4S4(SC6F5)4]2-
Noda,Aono,Okura
, p. 119 - 122 (2008/10/08)
The [Fe4S4(SC6F5)4]2- cluster with the electron-withdrawing terminal ligand, pentafluorobenzenethiolate, was synthesized and applied to the photoinduced electron transfer between Ru(bpy)su
Ground- and excited-state electron-transfer reactions: Photoinduced redox reactions of poly(pyridine)ruthenium(II) complexes and cobalt(III) cage compounds
Mok, Chup-Yew,Zanella, Andrew W.,Creutz, Carol,Sutin, Norman
, p. 2891 - 2897 (2008/10/08)
Rate constants for the quenching of poly(pyridine)ruthenium(II) (RuL32+) excited states by caged cobalt(III) amine complexes (Co(cage)3+) range from 2 × 108 to 1 × 109 M-1 s-1 at 25°C. The quenching process involves parallel energy transfer (ken ～ 1 × 108 M-1 s-1) and electron transfer (kel = (0.1-1) × 109 M-1 s-1) from *RuL32+ to Co(cage)3+. The rate constants for electron-transfer quenching are consistent with expectations based on an adiabatic semiclassical model. The yields of electron-transfer products range from 0.3 to 1.0, increasing as the rate constants for the back-reaction of RuL33+ with Co(cage)2+ diminish. The relatively low magnitudes of the back-reaction rate constants, (0.08-8) × 108 M-1 s-1, are consistent with the high yields of electron-transfer products and derive from poor coupling of the RuL33+ and Co(cage)2+ orbitals.
