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 shifting terrain of feminist theory and activism : university-based women's centres and third wave feminism

This thesis, based on the results of an organizational ethnography of a university-based feminist organization in Southern Ontario (the Centre), traces how third wave feminism is being constituted in the goals, initiatives, mandate, organizational structure, and overall culture of university-based feminist organizations. I argue that, from its inception, the meanings and goals of the Centre have been contested through internal critique, reflection, and discussion inspired by significant shifts in feminist theory that challenge the fundamental principles of second wave feminism. I identify a major shift in the development and direction of the Centre that occurs in two distinct phases. The first phase of the shift occurs with the emergence of an antioppression framework, which broadens the Centre's mandate beyond gender and sexism to consider multiple axes of identity and oppression that affect women's lives. The second phase of this shift is characterized by a focus on (trans) inclusion and accessibility and has involved changing the Centre's name so that it is no longer identified as a women's centre in order to reflect more accurately its focus on mUltiple axes of identity and oppression. Along with identifying two phases of a major shift in the direction of the Centre, I trace two discourses about its development. The dominant discourse of the Centre's development is one of progress and evolution. The dominant discourse characterizes the Centre as a dynamic feminist organization that consistently strives to be more inclusive and diverse. The reverse discourse undermines the dominant discourse by emphasizing that, despite the Centre's official attempts to be inclusive and to build diversity, little has actually changed, leaving women of colour marginalized in the Centre's dominant culture of whiteness. This research reveals that, while many of their strategies have unintended (negative) consequences, members of the Centre are working to build an inclusive politics of resistance that avoids the mistakes of earlier feminist movements and organizations. These members, along with other activists, actively constitute third wave feminism in a process that is challenging, contradictory, and often painful. A critical analysis of this process and the strategies it involves provides an opportunity for activists to reflect on their experiences and develop new strategies in an effort to further struggles for social justice and equity.

An examination of the effects on learning seen in children afforded the opportunity to control the order of repetitions for three novel spatiotemporal sequences

Children were afforded the opportunity to control the order of repetitions for three novel spatiotemporal sequences. The following was predicted: a) children and adults in the self-regulated (SELF) groups would produce faster movement (MT) and reaction times (R T) and greater recall success (RS) during retention compared to the age-matched yoked (YOKE) groups; b) children would choose to switch sequences less often than adults; c) adults would produce faster MT and RT and greater RS than the children during acquisition and retention, independent of experimental group. During acquisition, no effects were seen for RS, however for MT and RT there was a main effect for age as well as block. During retention a main effect for practice condition was seen for RS and failed to reach statistical significance for MT and RT, thus partially supporting our first and second hypotheses. The third hypothesis was not supported.