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• W2560890717 abstract "The chemistry of metal nitrido complexes has received much attention in recent years. This thesis describes the kinetics and mechanisms of the reactions of [Ru(N)(salchda)(MeOH)]+ and [Os(N)(salchda)(H2O)]+ (salchda = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion) with L-ascorbic acid, sulfite, hydroxide and L-cysteine in aqueous media. The oxidation of L-ascorbic acid (H2A) by [RuVI(N)(salchda)(MeOH)]+ (RuVIN) has been studied in aqueous acidic solutions from pH range of 1 to 6 under argon atmosphere. The reaction has the following stoichiometry: 2RuVIN + 3H2A → 2[RuIII(NH2-HA)]+ + A. The pseudo-first-order rate constant, kobs, depends linearly on the concentration of H2A. The second-order rate constants, k2 are dependent on [H+] according to the relationship k2 = (ka[H+] + kbKa) / ([H+] + Ka), where ka and kb are the rate constants for the oxidation of H2A and HA-, respectively. At 298.0 K and I = 0.1 M, ka = (6.47 ± 6.25) × 101 M-1 s-1, kb = (4.84 ± 0.10) × 103 M-1 s-1 and Ka = (4.23 ± 0.40) × 10-5. Kinetic studies have also been carried out in D2O. The solvent kinetic isotope effects are 3.32 and 0.98 for ka and kb, respectively. Mechanisms involving HAT/N-rebound at low pH (≤ 2) and nucleophilic attack at the nitrido at high pH (≥ 5) are proposed. The kinetics of oxidation of sulfite (SIV, SO32- + HSO3-) by [RuVI(N)(salchda)(MeOH)]+ (RuVIN) and [OsVI(N)(salchda)(H2O)]+ (OsVIN) have been studied in aqueous solutions. For the oxidation of SIV by RuVIN, the rate law is -d[RuVIN]/dt = k2[RuVIN][SIV]. The second-order rate constant, k2, is found to be pH dependent with k2 = (ka[H+] + kbKa)/([H+] + Ka), where ka and kb are the rate constants for the oxidation of HSO3- and SO32-, respectively. At 298.0 K and I = 1.0 M, ka = (1.63 ± 0.92) × 102 M-1 s-1 and kb = (6.17 ± 0.02) × 106 M-1 s-1, respectively. For OsVIN, the reaction has the following stoichiometry: [OsVI(N)]+ + SO32- + 2H+ → [OsIV(NH2SO3)]+. The rate law is -d[OsVIN]/dt = k2[OsVIN][SIV]. The dependence of k2 on [H+] shows a similar relationship with ruthenium(VI) nitrido where ka' and kb' were found to be (2.79 ± 0.97) × 10-1 M-1 s-1 and (1.14 ± 0.03) × 101 M-1 s-1 respectively at 298.0 K and I = 1.0 M. For both RuVIN and OsVIN, sulfite undergoes nucleophilic attack at the nitrido ligand to afford the sulfamato species, [RuIII(NH2SO3)(salchda)(OH2)] and [OsIV(NH2SO3)(salchda)(OH2)]+, respectively. Details of the reaction mechanism will be discussed. The reactions of RuVIN and OsVIN with hydroxide (OH-) have been studied in aqueous alkaline solutions. For RuVIN, the reaction has the following stoichiometry: RuVIN + 2OH- → RuIINO + H2O. The rate law is -d[RuVIN]/dt = k2[RuVIN][OH-]. It is proposed that OH- undergoes nucleophilic attack at the nitrido ligand to afford the nitrosyl species, RuII(NO)(salchda)(OH). For OsVIN, the reaction follows the rate law -d[OsVIN]/dt = k2[OsVIN][OH-]. The mechanism involves initial N∙∙∙N coupling of [OsVI(N)(L)(OH)], followed by N2 releasing and attacked by another OH- to form the peroxo species, Os(O2)(salchda). The oxidation of L-cysteine (Cys) by [RuVI(N)(salchda)(MeOH)]+ has been studied in anaerobic aqueous solutions over the pH range of 1.00-5.32. The electrophilic ruthenium nitrido species undergoes stepwise reactions with L-cysteine to produce the sulfilamido ([RuIV(NH)(Cys)(salchda)]+), sulfilamine ([RuIII(NH2)(Cys)(salchda)]+), and amine ([RuIII(NH3)(salchda)]+) complexes of ruthenium. At low pH (pH ≤ 4), only two phases were observed. However, three phases were observed at high pH (pH ≥ 4). The rate laws for all three phases are phases were observed at high pH (pH ≥ 4). The rate laws for all three phases are 0.09) × 105 M-1 s-1, k2' = (1.78 ± 0.21) × 102 M-1 s-1, and k2'' = (6.52 ± 0.30) × 101 M-1 s-1 at pH = 5.32, T = 298.0 K and I = 0.1 M for the first, second, and third phase respectively. The dependence of k2 on [H]+ indicated that both protonated (Cys-H+) nd neutral species (Cys) are involved in the reaction with the relationship k2 = (ka[H+] + kbKa) / ([H+] + Ka), where ka and kb are the rate constants for the oxidation of Cys-H+ and Cys, respectively. The reactivity of Cys is almost 103 times greater than that of Cys-H+. Kinetic studies have also been carried out in D2O. For the first phase, the solvent kinetic isotope effects are 2.03 and 1.74 at pH = 1.0 and 5.4, respectively. For the second phase, the solvent kinetic isotope effect (ka'(H2O)/ka'(D2O) is 2.52 at pH = 1.0. For the third phase, the solvent kinetic isotope effect (ka(H2O)/ka(D2O) is 2.27 at pH = 5.4. Hydrogen atom transfer (HAT) mechanisms are proposed at low pH." @default.
• W2560890717 created "2017-01-06" @default.
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• W2560890717 date "2015-01-01" @default.
• W2560890717 modified "2023-09-24" @default.
• W2560890717 title "Kinetics and mechanisms of some redox reactions of nitridoruthenium(VI) and nitridoosmium(VI) complexes bearing a salen ligand in aqueous solutions" @default.
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