Synthesis of several interrelated metallo-compounds is described. They are of intrinsic interest in their own right and were designed as intermediates and model studies for construction of various acetylene metal systems with interesting synthetic and optical potential. Synthesis of a triacetal and its eta6-tricarbonylchromium(0) complex 31 is described. Further transformations towards an eneyne derivative of 31 were complicated by the inherent instability of the complex towards oxidative decomplexation. Synthesis of a series of hexa-substituted eta 6-tricarbonylchromium(0) complexes 39--47 (E = H, Me, SiMe3, SnMe3, Cl, Br, I, COH, CO2Me) and 54--57 (E = H, Cl, Br, I) by di- or tri-lithiation of the parent compounds followed by quenching with a series of electrophiles is reported. Attempts to obtain alkynylated derivatives of the complexes by Sonagashira coupling reactions failed to produce the desired products. A novel tridurylborane 83, incorporating three azulenyl substituents, was prepared and displayed unique photophysical properties with an absorption maximum nearly 80 nm longer than that of its precursor. A new class of heteroatom-containing triarylboranes 79 (R = OMe) and 96 (R = Me) were synthesized. Triarylborane 96 displayed broadened resonances in the 1H NMR spectrum at room temperature and a low-temperature 1H NMR study revealed that the borane existed as an approximate 10:1 ratio of two enantiomeric sets of conformational isomers. Triarylborane 96 was further extended by sequential Sonagashira coupling reactions to yield the highly fluorescent chromophore 110, which exhibited intense and long-wave absorption and emission maxima.
| Identifer | oai:union.ndltd.org:uottawa.ca/oai:ruor.uottawa.ca:10393/26403 |
| Date | January 2003 |
| Creators | Tiffin, Jenny L |
| Contributors | Fallis, Alex G., |
| Publisher | University of Ottawa (Canada) |
| Source Sets | Université d’Ottawa |
| Language | English |
| Detected Language | English |
| Type | Thesis |
| Format | 111 p. |
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