Kinetic and product studies for the oxidtion of organic sulfides and sulfoxides in the presence of transition metal complexes

Rates and products of the oxidation of diphenyl sulfide, phenyl methyl sulfide, p-chlorophenyl methyl sulfide and diphenyl sulfoxide have been determined. Oxidants included t-Bu02H alone, t-Bu02H plus molybdenum or vanadium catalysts and the molybdenum peroxo complex Mo0(02)2*HMPT. Reactions were chiefly carried out in ethanol at temperatures ranging from 20° to 65°C. Oxidation of diphenyl sulfide by t-Bu02H in absolute ethanol at 65°C followed second-order kinetics with k2 = 5.61 x 10 G M~1s"1, and yielded only diphenyl sulfoxide. The Mo(C0)g-catalyzed reaction gave both the sulfoxide and the sulfone with consecutive third-order kinetics. Rate = k3[Mo][t-Bu02H][Ph2S] + k^[Mo][t-Bu02H][Ph2S0], where log k3 = 12.62 - 18500/RT, and log k^ = 10.73 - 17400/RT. In the absence of diphenyl sulfide, diphenyl sulfoxide did not react with t-Bu02H plus molybdenum catalysts, but was oxidized by t-Bu02H-V0(acac)2. The uncatalyzed oxidation of phenyl methyl sulfide by t-Bu02H in absolute ethanol at 65°C gave a second-order rate constant, k = 3.48 x 10~"5 M^s""1. With added Mo(C0)g, the product was mainly phenyl methyl sulfoxide; Rate = k3[Mo][t-Bu02H][PhSCH3] where log k3 = 22.0 - 44500/RT. Both diphenyl sulfide and diphenyl sulfoxide react readily with the molybdenum peroxy complex, Mo0(02)2'HMPT in absolute ethanol at 35°C, yielding diphenyl sulfone. The observed features are mainly in agreement with the literature on metal ion-catalyzed oxidations of organic compounds by hydroperoxides. These indicate the formation of an active catalyst and the complexation of t-Bu02H with the catalyst. However, the relatively large difference between the activation energies for diphenyl sulfide and phenyl methyl sulfide, and the non-reactivity of diphenyl sulfoxide suggest the involvement of sulfide in the production of an active species.

The Effects of Perceived Product-Association Incongruity on Consumption Experiences

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Exploring Teacher Candidates’ Perception of Practicum Placement Within Concurrent Teacher Education in Two Ontario Universities

In this study, teacher candidates’ perception of their concurrent education program at two Ontario universities were examined, with specific emphasis on how the programs utilized practicum placements, to determine the effectiveness in preparing teacher candidates to teach. This research also strived to uncover the best ways to optimize concurrent teacher education through practicum placements. A questionnaire and interviews were used to uncover teacher candidates’ perceptions at one teacher education program that used full integration of practicum and one that used minimal integration of practicum. The findings revealed that teacher candidates were generally more satisfied with the overall program when there was full integration of practicum. There were statistically significant differences found between the two concurrent programs with regard to practicum time and preparedness and context of the practicum and a highly significant difference found for theory-practice divide. There was also a statistically significant difference (p < .05) observed between the teacher candidates at each university in terms of their beliefs about the need for improvement of their program. Some of the improvements that participants believed could be made to their respective programs included having (a) exceptional mentor teachers and teacher educators, (b) longer placements with a balance of observation and practicum teaching, (c) clear expectations and evaluations of practicum placement, and (d) more distinct connections between theory and practice made within the programs.