Some aspects of the chemistry of 1, 3, 4 - Thiadiazolium salts and related compounds

The work described in this thesis has been divided into seven sections. The first section involves the preparation of N'-acyl-N'-arylN- benzothiohydrazides by the acylation of N'-aryl-N-benzothiohydrazides and is followed by a brief discussion of their possible conformation in solution. The second section deals with the preparation of 1,3,4-thiadiazolium salts by the action of perchloric acid/acetic anhydride on N'-acylN'- aryl-N-benzothiohydrazides and also by the reaction of N'-arylN- benzothiohydrazides with nitriles in an acidic medium. The preparation of 2-methylthio-I,3,4-thiadiazolium methosulfate by methylating the corresponding thione is also described. The third section deals with the reaction of 2-phenyl- and 2-methyl-I,3,4-thiadiazolium salts with alcohols in the presence of base. The stability and spectra of these compounds are discussed. Treatment of the 2-methyl-I,3,4-thiadiazolium salt with base was found to give rise to a dimeric anhydrobase and evidence supporting its structure is given. The anhydrobase could be trapped by a variety of acylating and thioacylating agents before dimerization occurred. In the fourth section, the reaction of N'-acyl-N'-aryl-N-benzothiohydrazides with a variety of acid anhydrides is described. These compounds were found to be identical with those obtained by acylating the anhydrobase. The mass spectral fragmentation of these compounds is described and the anomolous product obtained upon thiobenzoylation of 3-methyl-l-phenyl-pyrazal-5-one is also discussed. The fifth section deals with thioacyl derivatives of the anhydrobase which were prepared by the action of phosphorus pentasulfide upon the oxygen analogues and also obtained as the major product of the reaction of thioacetic acid with compounds related to N'-aryl-N-benzothiohydrazides. The mass spectra and p.m.r. spectra of these compounds are discussed. In the sixth section, the reaction of the 2-methylthio-l,3,4- thiadiazolium salt with active methylene compounds to give acyl and diacyl derivatives of the anhydrobase is described. Some aspects of these compounds are discussed. The seventh section describes the synthesis of ncyanine~' type dyes incorporating the l,3,4-thiadiazole ring and their spectra are briefly discussed.

The red book of Niagara : a comprehensive guide to the scientific, historical and scenic aspects of Niagara for the use of travellers /

Includes bibliographical references and index.

An analysis of the systemic aspects of rights training for people with intellectual disabilities

Individuals with intellectual disabilities (ID) as a group have been subject to abuse. Individuals with ID need to be made aware of their rights. The 3Rs: Rights, Respect and Responsibility Human Rights Project is promoting rights awareness in individuals with ID, their caregivers and family members. To be effeCtive, abuse prevention must include support from the whole organization and its processes. This research evaluated the impact of the 3Rs initiative on the organization. It focused particularly on descriptions of organizational change perceived by full-time staff and managers in response to the initiation of the 3Rs Project. Behavioural interviews were conducted and a thematic analysis was used to describe changes in the organizational culture and behavioural mechanisms maintaining these changes. Systemic barriers to change were also explored. The results indicate that the Association is effectively implementing and supporting the rights-based philosophy.

Death anxiety and experiences of transcendence : peak experiences of skydivers

Terror Management Theory (TMT) suggests that human beings battle to protect ourselves from the potential terror resulting from the juxtaposition of our need for selfpreservation and our unique human ability to realize that we cannot avoid death. Over 150 studies have shown that when people are primed with the awareness of mortality they grasp onto their cultural world view more tenaciously than when they are primed with another unpleasant stimulus (i.e., show "cultural world view defense"). Applying the principles ofTMT, the first purpose of the present research was to examine whether the amount of peak experiences reduce the tendency to show cultural world view defense (an indicator of unconscious death fear) after a death prime. The second purpose was to examine a new model of implicit spirituality, by testing proposed relationships between implicit spirituality, peak experiences and intrinsic religiosity, and by testing whether peak experiences and/or intrinsic religiosity mediate the relationship between implicit spirituality and conscious and/or unconscious death fears. Skydivers were chosen as the primary participants for this research because of their unique characteristics in the context of TMT research. Previous research suggests that veteran skydivers have peak experiences as they skydive, and I assumed that their peak experiences would not be influenced by intrinsic religious beliefs. Novice skydivers may have their implicit spirituality brought forth because of their proximity to possible death. The willingness of both groups to place themselves close to death allowed their reactions to unconscious and conscious death fears to be assessed in a real setting. Novice skydivers' proximity to death made them an ideal group to study to see whether intrinsic religiosity mediated the relationship between their implicit spirituality and conscious and/or unconscious death fears. One hundred and twenty-five people participated in this research: 38 veteran and 46 novice skydivers, as well as 41 people who accompanied them to the drop zone. Of these, 23 veterans, 19 novices, and 22 friends returned a follow-up packet of questionnaires three weeks later. As expected, the veterans' unconscious death fear scores remained stable from pre-jump to post-jump (after the death prime), and three weeks later, whereas the novices' scores increased, but only marginally. As predicted, the novice skydivers' implicit spirituality was significantly higher than the veterans' and was negatively correlated with their conscious death fear, which was not mediated by their intrinsic religiosity. Only the novices' follow-up (trait) implicit spirituality correlated negatively with their pre-jump unconscious death fear. Among both groups of skydivers, there were significant relationships between implicit spirituality and peak experiences, and although the novices were significantly higher on peak experiences after the jump, peak experiences did not mediate the relationship between implicit spirituality and unconscious death fear for either group. In both groups follow-up intrinsic religiosity correlated with implicit spirituality. Peak experiences and intrinsic religiosity were not related with one another, suggesting that these are different ways of accessing an implicit spirituality. Results imply that implicit spirituality was brought forth (in the case of novice skydivers who were consciously close to death) and can be accessed through both peak experiences and intrinsic religiosity.

Father involvement in the breastfeeding process : determining contributing aspects

The importance of father involvement in the young family is increasingly evident. This research was conducted using the theory of planned behaviour to understand important aspects contributing to father invo lvement in the breastfeeding process. Eighty mothers and 65 fathers of one-year-old children completed a questionnaire regarding father involvement (FI) in breastfeeding. Measures included attitudes, subjective norms, and perceived behaviour control regarding FI and the extent to which fathers demonstrated involvement by advocating for and affIrming breastfeeding, being present during breastfeeding, providing household help, and being responsive to their partners' needs. Results suggest that mothers and fathers experience FI differently. Mothers' perceptions are motivated by intrinsic attitudinal considerations, whereas fathers' involvement is primarily motivated by the opinions of others. Interventions should focus on increasing fathers' perception of societal approval through approaches such as peer-led groups, and increasing mothers' approval through information of the value of fathers' involvement in the breastfeeding process.

Molybdenum (IV) imido silylamido and hydride complexes : stoichiometric and catalytic reactivity, mechanistic aspects of hydrosilation reactions

This thesis describes the synthesis, structural studies, and stoichiometric and catalytic reactivity of novel Mo(IV) imido silylamide (R'N)Mo(R2)(173_RIN-SiR32-H)(PMe3)n (1: Rl = tBu, Ar', Ar; R2 = Cl; R32 = Me2, MePh, MeCl, Ph2, HPh; n = 2; 2: R' = Ar, R2 = SiH2Ph, n = 1) and hydride complexes (ArN)Mo(H)(R)(PMe3)3 (R = Cl (3), SiH2Ph (4». Compounds of type 1 were generated from (R'N)Mo(PMe3)n(L) (5: R' = tBu, Ar', Ar; L = PMe3, r/- C2H4) and chlorohydrosilanes by the imido/silane coupling approach, recently discovered in our group. The mechanism of the reaction of 5 with HSiCh to give (ArN)MoClz(PMe3)3 (8) was studied by VT NMR, which revealed the intermediacy of (ArN)MCh(172 -ArN=SiHCl)(PMe3)z (9). The imido/silyl coupling methodology was transferred to the reactions of 5 with chlorine-free hydrosilanes. This approach allowed for the isolation of a novel ,B-agostic compound (ArN)Mo(SiHzPh)(173 -NAr-SiHPhH)(PMe3) (10). The latter was found to be active in a variety of hydrosilation processes, including the rare monoaddition of PhSiH3 to benzonitrile. Stoichiometric reactions of 11 with unsaturated compounds appear to proceed via the silanimine intermediate (ArN)M(17z-ArN=SiHPh)(PMe3) (12) and, in the case of olefins and nitriles, give products of Si-C coupling, such as (ArN)Mo(R)(173 -NAr-SiHPh-CH=CHR')(PMe3) (13: R = Et, R' = H; 14: R = H, R' = Ph) and (ArN)Mo(172-NAr-SiHPh-CHR=N)(PMe3) (15). Compound 13 was also subjected to catalysis showing much improved activity in the hydrosilation of carbonyls and alkenes. Hydride complexes 3 and 4 were prepared starting from (ArN)MoCh(PMe3)3 (8). Both hydride species catalyze a diversity of hydrosilation processes that proceed via initial substrate activation but not silane addition. The proposed mechanism is supported by stoichiometric reactions of 3 and 4, kinetic NMR studies, and DFf calculations for the hydrosilation of benzaldehyde and acetone mediated by 4.

Revisiting the Jewish American princess : Jewish girls, the J.A.P. discursive stereotype, and negotiated identity

This qualitative exploratory research investigates how Canadian Jewish girls understand the discursive stereotype of the Jewish American Princess (JAP), and how they take up these understandings of the J AP in relation to their identities. Three focus groups and six interviews were conducted with girls attending Jewish high schools in Toronto, Canada to explore these questions. From a third wave Jewish feminist perspective, and taking a mediated action approach to identity, two analyses were conducted. A thematic analysis of peer relations, gender, community, and religious understandings demonstrates how aspects of individual identities mediate interpretations of the JAP. A series ofpor t rai t s of JAP-related identity were constructed to analyze how the JAP discursive stereotype also functions as a cultural tool that is taken up by the participants to mediate expressions of their identities. These findings establish the contradictory ways these Jewish girls describe, interpret, and utilize the JAP discursive stereotype, and the complex roles it plays in their social worlds.