Novel A-A and A-B difunctional monomers were synthesized by utilizing Reissert compound chemistry and via the use of bis(α-aminonitrile)s. These monomers were produced in high yields with preformed heterocyclic nuclei which included benzothiazole, isoquinoline and quinoline. Acylated linear polyamine derivatives were obtained by the step growth condensation polymerization of open chain bis(Reissert compound)s with suitable dihaloalkanes; intrinsic viscosities of up to 0.48 dl/g were obtained in unoptimized runs. The constitutional repeat unit of these polymers consists of four independent structural variables and thus provides versatility for tailor made macromolecular syntheses. Novel bis(Schiff base) monomers based on 1,4-trans-diamino cyclohexane were synthesized and these could be used either directly in the production of poly(azomethine aryl ether)s or synthesis of diamines and dicarboxylic acids containing the trans cyclohexyl moiety. Novel aromatic diamine based bis(α-aminonitrile)s were synthesized from commercially available diamines and are currently being used in the syntheses of post-reaction modifiable co-polyamides. A novel and unique product of rearrangement of benzothiazole Reissert compounds was isolated and characterized. It was postulated that the reaction proceeds via a bimolecular reaction between 2-cyanobenzothiazole and the’ ring opened azomethinethiophenoxide followed by an intramolecular acyl transfer and eventual reaction with methyl iodide leading to a novel benzothiazine. A novel nucleophilic aromatic substitution reaction was discovered which involved the reaction of a masked carbonyl carbanion synthon with activated aromatic fluorides. Hitherto unknown poly(aryl ketone sulfone)s were synthesized when this chemistry was extended with the use of bis(α-aryl aminonitrile)s. A novel quinodimethane was synthesized in quantitative yield by an intramolecular dehydrocyanation. Its structural features are unique in that one end is substituted by a donor moiety while the other end is captodative: this makes it attractive in the fields where electrical conductance and non linear optical (NLO) applications are important. / Ph. D.

Thermal reactions of the iridium complex, [Ir(COD)(PMe₃)₃]Cl (COD=1, 5 Cyclooctadiene), with benzene, benzaldehyde, pyridine, and furan yield the C-H addition products of mer-(Me₃P)₃Ir(Phenyl)(H)C! (1), mer-(Me₃P)₃Ir(COC₆H₅)(H)Cl (II), mer-(Me₃P)₃Ir(Pyridyl)(H)Cl (IID, and mer-(Me₃P)₃Ir(furyl)Cl (IV), respectively. Each of these complexes was characterized by 1H, 13C, 31P NMR spectroscopy and single crystal X-ray diffraction. Thermal reaction of the [Ir(COD)(PMe₃)₃]CI with thiophene and benzothiophene produced the C-S addition products forming thiometallacycles of (Me₃P)₃Ir-(CH=CHCH=CHS)CI(V), and (Me₃P)₃Ir(CH=CH-C₆H₄S)Cl (VI). The C-H addition products are unreactive and require the aid of TI[PF6] to remove the chloride ligand to provide an open coordination site. Complex (I) and 3,3-dimethyl-1-butyne, produced a 1,4-di-t-butyldienyl complex (VIII) by a double insertion of the alkyne with one t-butyl group forming an agostic interaction with iridium. Deuterium labeling experiments revealed the mechanism to involve: initial acetylene coordination after the chloride ligand was removed by TI⁺ followed by a hydride migration forming a vinyl complex and allowing a second alkyne to coordinate, rearrangement of the second alkyne into a vinylidene and finally a migratory-insertion of the vinyl group unto the vinylidene to form (VIII). Complex (III) and two equivalence of 3,3-dimethyl-1-butyne produced a trans diacetylide complex (XII). The pyridyl ligand was able to remove acidic protons via the nitrogen lone pair, thus altering the course of the reaction. Initial investigations have led to a possible mechanism. Complex (IV) and 3,3-dimethyl-1-butyne gave an interesting hydrido metallo-vinyl complex (XIV) with the t-butyl group forming an agostic CH-Ir interaction. A deuterium labeling experiment revealed the alkyne to initially coordinate and rearrange into a vinylidene, followed by migratory-insertion of the furan group unto the vinylidene to give (XIV). The furyl group is believed to stabilize the initial intermediate by forming a five coordinate square pyramidal complex through the donation of a pair of electrons from the oxygen atom. Reductive elimination of (XIV) using elevated temperatures gave exclusively the trans 3,3-dimethyl-1-(2 furanyl) -1-butyne (XV). The resonance structure found in (IV) is the most important feature of this work. While most insertions occur between the M-H bond, the resonance structure found in (IV) provides the necessary means for insertion of unsaturates to occur between the M-C bond, leaving the M-H bond intact. In conclusion, it appears that the reactivity of the phenyl complex (I) is dependent on the alkyne used. While the reactivity of the pyridyl complex (III) is governed by the nitrogen lone pair; the reactivity of the furanyl complex (IV) follows a different pathway due to resonance stability of the furanyl ligand. / Ph. D.

Ng Mei Chu, Debbie. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references (leaves 135-143). / Abstracts in English and Chinese. / Abstract --- p.i / Acknowledgements --- p.iii / Prologue --- p.1 / Chapter Chapter I --- Technique in the light of Traite --- p.4 / Chapter Chapter II --- Visions --- p.31 / Chapter Chapter III --- Messiaen's Techniques in Visions --- p.31 / Chapter 1. --- Rhythmic Innovations / Chapter 2. --- Modes of Limited Transposition / Chapter 3. --- Invented Chords and Chord Progressions / Epilogue --- p.86 / Musical Examples --- p.89 / Appendices --- p.130 / Selected Bibliography --- p.135

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This is a rhetorical criticism of the science fiction short story, "Profession," by Isaac Asimov. Primary focus is on Asimov's persuasive use of this message to influence potentially creative young people to consider technological careers. A brief synopsis of the story is given, along with a statement of the functional role of science fiction in accustoming individuals to societal changes resulting from technological advancements.Methodology is based upon Kenneth Burke's dramatism which views human action in terms of a drama. Burke's concepts of identification and occupational psychosis are used in discovering the rhetor's use of persuasive strategies. Burke's pentad is used for analysis of significant ratios. The dominance of the act-scene ratio is demonstrated by the supremacy of action over motion.Asimov's work shows the influence of a philosophy of realism, identifiable by the featuring of the pentadic term "act." Asimov's primary motives are identified as a desire to share his belief in the benefits of technology and his own need for creative self-expression. / Department of Speech Communication

Thesis (M.A.)--University of Regina, 1997. / Includes bibliographical references (leaves 109-116).

Abbie Griffin, John R. Hauser. / "October 1991; revised February 1992." / Includes bibliographical references (p. 43-50).

by S.R. Connors. / "January 1992." / Includes bibliographical references (p. 21-22).

Olivier Messiaen's compositions for voice, though less widely known than his instrumental works, span some forty years and comprise a fifth of his total output. They have hitherto not been subject to much attention. A study of the elements comprising the vocal lines and accompanying instrumentation from the piano-voice song set, Trois melodies (1930), to the vast orchestral-choral La Transfiguration de Notre Seigneur Jesus-Chlist (1969) reveals, amongst other characteristic and evolving features, the emergence of a unique, simulated, plainchant style and its subsequent transformation into incantation with suitably modified accompaniment. While wide-ranging, chromatic and rhythmically free vocal lines are typical of many twentieth century compositions, Messiaen's use of such features is found to be novel, by virtue of the peculiar modal and temporal ambits within which he operated. Vocal delivery is progressively expanded from conventional bel canto production to humming, howling,and eventually speech and percussive sounds and reaches an apotheosis in the virtuoso effects of Cinq Rechants (1949). This recedes somewhat in La Transfiguration, which displays instead a wealth of hybrid plainsong-type writing. Choral works are interesting in that the emphasis shifts from standard part-writing to monody or accompanied unison singing, with an attendant absence of characterised solo parts. By constantly varying the colour of the single melodic line with different permutations of voice types, timbre assumes a new importance, particularly in La Transfiguration. The study of the texts, most of which were conceived by the composer simultaneously with the music, contributes much to the understanding of each work. Biblical symbolism in the early lyrics is progressively enriched by references to numerological, mythological and nature symbolism, mixed in an increasingly Surrealistic manner. The gradual incorporation of emotive phonemes in the texts, culminates in the invented language of Cinq Rechants. The thesis thus reveals an evolving yet persistently idiosyncratic vocal style, which establishes Messiaen as one of the most original composers of his time. It further demonstrates that his vocal works are an important component of his total oeuvre and also a significant contribution to twentieth century vocal literature.