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DC Field | Value | Language |
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dc.contributor.advisor | McGlinchey, M.J. | en_US |
dc.contributor.author | Tan, Teong-Seng | en_US |
dc.date.accessioned | 2014-06-18T16:43:17Z | - |
dc.date.available | 2014-06-18T16:43:17Z | - |
dc.date.created | 2010-12-22 | en_US |
dc.date.issued | 1976-03 | en_US |
dc.identifier.other | opendissertations/3761 | en_US |
dc.identifier.other | 4778 | en_US |
dc.identifier.other | 1709071 | en_US |
dc.identifier.uri | http://hdl.handle.net/11375/8566 | - |
dc.description.abstract | <p>A series of substituted bis(fluorobenzene)chromium complexes, (C₆H₄FX)₂Cr, where X is ortho, meta and para H, F, Cl, CH₃ and CF₃, have been synthesized by cocondensing chromium atoms and fluoroarenes. The ¹⁹F n.m.r. chemical shifts of these compounds correlate well with those of the corresponding C₆F₅X system suggesting that the overall electron-withdrawing effect of a π-bonded chromium atom is similar to the effect of four ring fluorine substituents.</p> <p>This correlation suggested that nucleophilic substitution reactions might be possible for fluorosubstituted bis(arene)chromium complexes; indeed bis(anisole) chromium was obtained in low yield from the reaction of bis{η-fluorobenzene)- chromium and sodium methoxide. Furthermore, a series of alkyl-and aryl-lithium reagents reacted readily with (C₆H₆)Cr(C₆F₆) at low temperature to yield polysubstituted products. Proton abstraction from the π-complexed C₆H₆ ring was a competing process and led to telomeric sandwich complexes of which several were identified spectroscopically.</p> <p>The behaviour of these complexes was consistent with the view that the π-{C₆H₆)Cr moiety donated electron density to the C₆F₆ ring and, to investigate this further, a series of complexes (C₆H₆)Cr(C₆F₅X) was prepared via the lithium reagent (C₆H₆)Cr(C₆F₅Li). These data supported the view of the π-complexed C₆F₅X system being more electron rich than the free C₆F₅X rings.</p> <p>These new sandwich complexes pose severe nomenclatural problems, and the CHROMARENE nomenclature has been proposed in an attempt to overcome these difficulties.</p> <p>Preliminary studies with other metals, viz., iron and germanium have provided direct routes to ferrocenophanes and organogermenes respectively.</p> | en_US |
dc.subject | Chemistry | en_US |
dc.subject | Chemistry | en_US |
dc.title | Metal Vapors in Synthesis: The Chemistry of Chromium Sandwich Complexes | en_US |
dc.type | thesis | en_US |
dc.contributor.department | Chemistry | en_US |
dc.description.degree | Doctor of Philosophy (PhD) | en_US |
Appears in Collections: | Open Access Dissertations and Theses |
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File | Size | Format | |
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fulltext.pdf | 5.19 MB | Adobe PDF | View/Open |
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