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DC Field | Value | Language |
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dc.contributor.advisor | McGlinchey, M.J. | en_US |
dc.contributor.author | Reginato, Nada | en_US |
dc.date.accessioned | 2014-06-18T17:02:17Z | - |
dc.date.available | 2014-06-18T17:02:17Z | - |
dc.date.created | 2009-08-27 | en_US |
dc.date.issued | 2003-05 | en_US |
dc.identifier.other | opendissertations/790 | en_US |
dc.identifier.other | 1808 | en_US |
dc.identifier.other | 976779 | en_US |
dc.identifier.uri | http://hdl.handle.net/11375/13070 | - |
dc.description.abstract | <p>This dissertation focuses on the synthesis, characterization and reactivity of several types of arene manganese systems.</p> <p>The reaction of potassium tert-butoxide with [(ɳ6-trindane)Mn(CO)3][BF4], 58c, was investigated in attempts to funtionalize 58c at the benzylic positions. It was demonstrated that complex 58c undergoes three C-H insertions and a haptotropic shift when treated with potassium tert-butoxide. As well, other trindane complexes including [(ɳ6-trindane)Mn(CO){O(OMe)3}2][BF4], 98, and [(ɳ6-trindane)Re(CO)3][PF6], 99, have been synthesized in hopes of alkylating the exo benzylic positions and develop an organometallic route to sumanene, a key fragment of C60 that has not yet been synthesized. The former compound, 98, was characterized by X-ray crystallography.</p> <p>In order to probe the generality of the novel reaction exhibited by the trindane system, other [(arene)Mn(CO)3]+ systems were studied in which the arene is bicyclic or tricyclic and possesses attached 5-, 6- or 7-membered rings. In particular, the syntheses of [(ɳ6-indane)Mn(CO)3][BF4], 84, [(ɳ6-tetralin)Mn(CO)3][PF6], 103, and [(ɳ6-dibenzosuberane)Mn(CO)3][BF4], 102, and their reactions with potassium tert-butoxide in the presence of donor ligands are presented. The products of these reactions were characterized by infrared and 1H, 13C and 31P NMR spectroscopy and mass spectrometry.</p> <p>The molecular dynamics of two hexaethylbenzene (HEB) complexes, [(ɳ6-HEB)Mn(CO)3][BF4], 147, and (ɳ6-HEB)Mn(CO)2Br, 148, were examined using low-temperature NMR spectroscopy. The activation barrier (ΔG≠) for ethyl rotation for 147 was determined to be ~ 11.5 kcal mol-1. Crystallographic data was obtained for 148, which demonstrated the 1,3,5-distal-2,4,6-proximal geometry, a feature common to transition metal HEB complexes.</p> <p>Finally, extended Hückel molecular orbital (EHMO) calculations were carried out for four polycyclic frameworks ligated to organometallic fragments: anti-dibenzpentalene, 157, and syn-dibenzpentalene, 158; fluoradenyl, 159, and fluoranthene, 160. Each of these systems exhibited unique dynamic behaviour, which are interpreted using a molecular orbital rationale.</p> | en_US |
dc.subject | Chemistry | en_US |
dc.subject | Chemistry | en_US |
dc.title | Polycyclic Compounds of Manganese | 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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fulltext.pdf | 8.96 MB | Adobe PDF | View/Open |
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