Search results for "Redox properties"
showing 7 items of 7 documents
Theoretical Study on the Photo-Oxidation and Photoreduction of an Azetidine Derivative as a Model of DNA Repair
2021
Photocycloreversion plays a central role in the study of the repair of DNA lesions, reverting them into the original pyrimidine nucleobases. Particularly, among the proposed mechanisms for the repair of DNA (6-4) photoproducts by photolyases, it has been suggested that it takes place through an intermediate characterized by a four-membered heterocyclic oxetane or azetidine ring, whose opening requires the reduction of the fused nucleobases. The specific role of this electron transfer step and its impact on the ring opening energetics remain to be understood. These processes are studied herein by means of quantum-chemical calculations on the two azetidine stereoisomers obtained from photocyc…
Chemistry and reactivity of dinuclear manganese oxamate complexes: Aerobic catechol oxidation catalyzed by high-valent bis(oxo)-bridged dimanganese(I…
2006
[EN] The high-valent bis(oxo)-bridged dimanganese(IV) complexes with the series of binucleating 4.5-X-2-o-phenylenebis(oxamate) ligands (opbaX(2); X = H, Cl, Me) (1a-c) have been synthesized and characterized structurally, spectroscopically and magnetically. Complexes la-c possess unique Mn-2(mu-O)(2) core structures with two o-phenylenediamidate type additional bridges which lead to exceptionally short Mn-Mn distances (2.63-2.65 angstrom) and fairly bent Mn-O-Mn angles (94.1 degrees-94.6 degrees). The cyclovoltammograms of la-c in acetonitrile (25 degrees C, 0.1 M Bu4NPF6) show an irreversible one-electron oxidation peak at moderately high anodic potentials (E-ap = 0.50-0.85 V versus SCE),…
Dicopper(II) Metallacyclophanes with Electroswitchable Polymethyl-Substitutedpara-Phenylene Spacers
2013
Double-stranded anionic dinuclear copper(II) metallacyclic complexes of the paracyclophane type [Cu2L2]4- have been prepared by the CuII-mediated self-assembly of different para-phenylenebis(oxamato) bridging ligands with either zero-, one-, or four-electron-donating methyl substituents (L=N,N′-para- phenylenebis(oxamate) (ppba; 1), 2-methyl- N,N′-para-phenylenebis(oxamate) (Meppba; 2), and 2,3,5,6-tetramethyl- N,N′-para-phenylenebis(oxamate) (Me4ppba; 3)). These complexes have been isolated as their tetra-n-butylammonium (1 a-3 a), lithium(I) (1 b-3 b), and tetraphenylphosphonium salts (1 c-3 c). The X-ray crystal structures of 1 a and 3 c show a parallel-displaced π-stacked conformation w…
The influence of pulsed redox conditions on soil phosphorus
2010
Abstract. The effects of eleven pulsed reduction-oxidation cycles (20 and 2 days, respectively) on soil phosphorus (P) dynamics are compared for 12 soils having contrasting properties and overfertilised with respect to P. Incubation conditions simulated transient waterlogging of the soil profile and involved repeated sampling and analysis of both the solution and solid phase P forms. An initial increase in P concentration occurred upto and including the fourth full cycle was followed by a sharp decline in concentration for all but one soil. Accompanying changes in the main extractable forms of P, which appeared to be cumulative, could be summarised as a general decline in the organic P frac…
The anion impact on the self-assembly of naphthalene diimide diimidazolium salts
2017
Naphthalene diimide diimidazolium salts differing in the anion nature were synthesized and their properties as well as their self-assembly behaviour were investigated. In particular, we took into consideration the N,N′-bis-(1-octyl-3-propylimidazolium)-naphthalene diimide cations and anions differing in size, shape and coordination abilities like [I−], [BF4−] and [NTf2−]. After determination of thermal behaviour, using differential scanning calorimetry and thermal gravimetric analysis, the electrochemical stability and redox properties were assessed using cyclic voltammetry. The self-assembly behaviour of the salts was investigated using concentration and temperature-dependent spectroscopic…
Chemistry and reactivity of mononuclear manganese oxamate complexes: Oxidative carbon-carbon bond cleavage of vic-diols by dioxygen and aldehydes cat…
2006
[EN] Two new mononuclear octahedral manganese(III) complexes with the tetradentate equatorial ligand o-phenylenebis(oxamate) (opba) and two aquo (1a) or two pyridine (1b) axial ligands have been synthesized and characterized structurally, magnetically, and electrochemically. The cyclovoltammogram of 1a in acetonitrile (25 degrees C, 0.1 M Bu4NPF6) shows an irreversible one-electron oxidation peak at a high anodic potential (E-ap = 1.03 V versus SCE), while that of 1b shows two well-separated one-electron oxidation peaks at moderate to high anodic potentials (E-ap = 0.92 and 1.27 V versus SCE), the first redox-wave being quasireversible in nature. The access to formally high-valent Mn-IV and…
[60]Fullerene l -Amino Acids and Peptides: Synthesis under Phase-Transfer Catalysis Using a Phosphine–Borane Linker. Electrochemical Behavior
2017
International audience; A new method to link amino acid and peptide derivatives to [60]fullerene is described. It uses hydrophosphination with a secondary phosphine borane. First, the stereoselective synthesis of secondary phosphine borane amino acid derivatives was achieved by alkylation of phenylphosphine borane with gamma-iodo-alpha-amino ester reagents under phase transfer catalysis (PTC). Second, a sec-phosphine borane amino ester was saponified and coupled with alpha,gamma-diamino esters to afford the corresponding dipeptide derivatives in good yields. Finally, the hydrophosphination reaction of [60]fullerene by the sec-phosphine borane compounds was performed under PTC to obtain C-60…