Half-sandwich Complexes of Ruthenium; Synthesis and Application to Catalysis

This thesis describes syntheses and catalytic reactivity of several half-sandwich complexes of ruthenium. The neutral ruthenium trihydride complex, Cp(PPri3)RuH3(1), can efficiently catalyse the H/D exchange reaction between various organic substrates and deuterium sources, such as benzene-d6. Moreover, the H/D exchange reactions of polar substrates were also observed in D2O, which is the most attractive deuterium source due to its low cost and low toxicity. Importantly, the H/D exchange under catalytic conditions was achieved not only in aromatic compounds but also in substituted liphatic compounds. Interestingly, in the case of alkanes and alkyl chains, highly selective deuterium incorporation in the terminal methyl positions was observed. It was discovered that the methylene units are engaged in exchange only if the molecule contains a donating functional group, such as O-and N-donors, C=C double bonds, arenes and CH3. The cationic half-sandwich ruthenium complex [Cp(PPri3)Ru(CH3CN)2]+(2) catalyses the chemoselective mono-addition of HSiMe2Ph to pyridine derivatives to selectively give the 1,4-regiospecific, N-silylated products. An ionic hydrosilylation mechanismis suggested based on the experiments. To support this mechanistic proposal, kinetic studies under catalytic conditions were performed. Also, the 1,4-regioselective mono-hydrosilylation of nitrogen containing compounds such as phenanthroline, quinoline and acridine can be achieved with the related Cp*complex [Cp*(phen)Ru(CH3CN)]+(3) (phen = 1,10-phenanthroline) and HSiMe2Ph under mild conditions. The cationic ruthenium complex 2 can also be used as an efficient catalyst for transfer hydrogenation of various organic substrates including carbonyls, imines, nitriles and esters. Secondary alcohols, amines, N-isopropylidene amines and ether compounds can be obtained in moderate to high yields. In addition, other ruthenium complexes, 1,3 and [Cp*(PPri3)Ru(CH3CN)2]+(4), can catalyse transfer hydrogenation of carbonyls although the reactions were sluggish compared to the ones of 2. The possible intermediate, Cp(PPri3)Ru(CH3CN)(H), was characterized by NMR at low temperature and the kinetic studies for the transfer hydrogenation of acetophenone were performed. Recently, chemoselective reduction of acid chlorides to aldehydes catalysed by the complex 2 was reported. To extend the catalytic reactivity of 2, reduction of iminoyl chlorides, which can be readily obtained from secondary amides, to the corresponding imines and aldehydes was investigated. Various substituted iminoyl chlorides were converted into the imines and aldehydes under mild conditions and several products were isolated with moderate yields.

The challenges and successful strategies of secondary school administrators /

This study presents information gathered during personal interviews in the area of challenges that administrators have faced in their careers, and the strategies they have found to be successful in meeting those challenges. This research is a qualitative study, using an inductive approach. Five participants were chosen, based on convenience sampling, with semi-structured interviews that were audio recorded. The theoretical research found that school violence and stafS'school morale were key challenges facing administrators, with a variety of approaches suggested to foster success in meeting those challenges. Some of these approaches included knowledge, team work, an ethic of care, and having a school vision. From the interviews it became clear that the challenges administrators faced included those posed by students, including disciplinary issues, those posed by adults and those posed by government changes in education. In regards to strategies for success, the interviews revealed three key concepts that were emphasized as vital. These were the assets of craft knowledge (experience), collegiality, and the use of other professional resources and educators.

A qualitative study of authority from the perspective of secondary school principals /

In this research study I examined how four principals of secondary schools interpreted authority and how these interpretations affected their practice. This study involved a presentation of the literature where the concept of qualitative methodology as well as general concepts of authority were reviewed. Four principals were interviewed and asked to reflect on their feelings and experiences as they related to the practice of authority. Five major themes emerged from their reflections and stories which were: Understandings of the Concept of Authority, Principals' Enactment of Authority, Thoughts and Experiences related to Challenges to Their Authority, A View of Principals' Challenge of Authority, and Changing Views on the Authority of Principals in Ontario. The stories of these four principals demonstrated that the practice of authority is complex, dynamic, and contains personal and social tensions. The sharing of these ideas and stories provided a window into the world of these secondary school educational leaders and their experiences with, and enactment of, authority. From this research four recommendations were made to improve educators' practice related to the issue of authority. The importance of this study is that it presents an understanding of the dynamic nature of the process and enactment of authority by these secondary school principals at a unique time in the history of education in Ontario.This qualitative research provides a snapshot of a particular group of educators at a particular time and place. Others need to add to these understandings and modify these ideas through further research. Understanding the experiences of educational leaders as they negotiate concepts of authority gives a window on this very complex, yet vital, component of education.

The investigation of the reduction mechanism of the 5a-reductase enzyme of Penicillium decumbens /

The 5a-reductase of Penicillium decumbens ATCC 10436 was used as a model for the mammalian enzyme to investigate the mechanism of reduction of testosterone to 5adihydrotestosterone . The purpose of this study was to search for specific 5a-reductase inhibitors which antagonize prostate cancer . In a whole-cell biotransformation mode, this organism reduced testosterone (1) to 5a-dihydrosteroids (8) and 5aandrostane- 3, 17-dione (9) in yields of 28% and 37% respectively. Control experiments have shown that 5aandrostane- 3, 17-dione (9) can be produced from the corresponding alcohol (8) in a subsequent reaction separate from that catalysed by the 5a-reductase enzyme . Androst-4- ene-3, 17-dione (2) is reduced to give only (9) with a recovery of 80% The stereochemistry of the reduction was determined by 500 MHz ^H NMR analysis of the products resulting from the deuterium labelled substrates. The results were obtained by an analysis of the NOE difference spectra, double-quantum filtered phase sensitive COSY 2-D spectra, and ^^c-Ir 2-D shift correlation spectra of deuterium labelled products. According to the unambiguous assignment of the signals due to H-4a and H-4Ii in 5a-dihydro steroids, the NMR data show clearly that addition of hydrogen to the 4{5)K bond has occurred in a trans manner at positions 413 and 5a. To Study the reduction mechanism of this enzyme, several substrates were prepared as following; 3-methyleneandrost-4-en- 17fi-ol(3), androst-4-en-17i5-ol(5) , androst-4-en-3ii, 17fi-diol (6) and 4, 5ii-epoxyandrostane-3, 17-dione (7) . Results suggest that this enzyme system requires an oxygen atom at the 3-position of the steroid in order to bind the substrate. Furthermore, the mechanism of this 5a-reductase may proceed via direct addition of hydrogen at the 4,5 position without involvement of a carbonyl group as an intermediate.

Study of the application of the high performance liquid chromatography-particle beam interface-mass spectrometry technique on some pesiticides and the reduction phenomena in the system

This work includes two major parts. The first part of the work concentrated on the studies of the application of the highperfonnance liquid chromatography-particle beam interface-mass spectrometry system of some pesticides. Factors that have effects on the detection sensitivity were studied. The linearity ranges and detection limits of ten pesticides are also given in this work. The second part of the work concentrated on the studies of the reduction phenomena of nitro compounds in the HPLC-PB-MS system. Direct probe mass spectrometry and gas chromatography-mass spectrometry techniques were also used in the work. Factors that have effects on the reduction of the nitro compounds were studied, and the possible explanation is proposed. The final part of this work included the studies of reduction behavior of some other compounds in the HPLC-PB-MS system, included in them are: quinones, sulfoxides, and sulfones.

A conceptual analysis of research literature on teachers' ideology and literacy practices: extending the dialogue through a secondary analysis of high school English as an additional language contexts /

This thesis provides a conceptual analysis of research literature on teachers' ideology and literacy practices as well as a secondary analysis of three empirical studies and the ways in which the ideologies of the English as an Additional Language (EAL) (Street, 2005) teachers in these contexts impact the teaching of literacy in empowering/disabling ways. Several major theoretical components of Cummins (1996, 2000), Gee (1996, 2004) and Street (1995, 2001) are examined and integrated into a conceptual triad consisting of three main areas: power and ideology, validation of students ' cultural and linguistic backgrounds, and teaching that empowers. This triad provides the framework for the secondary analysis of three empirical studies on the ideologies of secondary EAL teachers. Implications of the findings from the conceptual and secondary analyses are examined in light of the research community and secondary school teachers of EAL.