The oxidative addition of the N-H bond of both heterocyclic and acyclic amines and the O-H bond of phenols, water and carboxylic acids to iridium(I) trimethylphosphines complexes was studied and the reactivity of the resulting hydrido amido-, aryloxo- and carboxylato iridium(III) complexes was investigated. Oxidative addition of the N-H bond of pyrrole, indole, 3-methylindole, 7-azaindole, carbazole and aniline to [Ir(COD)(PMe₃)₃]CI (<b>1a</b>) (COD = 1,5-cyclooctadiene) produces merIr( NR₂)H(PMe₃)₃CI (<b>2a-f</b>) complexes. That these amines were bound to iridium through an Ir-N bond was established by ¹H, ³¹P and ¹³C NMR spectroscopy, IR spectroscopy, C-H analyses and single crystal x-ray diffraction. Similarly, oxidative addition of the O-H bond of phenol, p-cresol, 3,5-dimethylphenol, and water to [Ir(COD)(PMe₃)₃]CI (la) produces mer-Ir(OR)H(PMe₃)₃C1 (<b>5a-c and 6</b>) which were characterized by ¹H, ³¹P and ¹³C NMR spectroscopy, C H analyses and single crystal x-ray diffraction. A preliminary study of the reactivity of both the amido and aryloxo complexes suggests that because of the increased electron affinity of the heteroatoms involved (N or 0), there is high electron density at the heteroatoms in these complexes and therefore the M-N or M-O bond can heterolyze more easily than M-C bonds. This increased tendency of the M-N or M-O bond to heterolyze leads to decomposition reactions when attempts are made to open up a coordination site at the metal center by removing the chloride ligand. / Ph. D.
| Identifer | oai:union.ndltd.org:VTETD/oai:vtechworks.lib.vt.edu:10919/39829 |
| Date | 13 October 2005 |
| Creators | Lapido, Folami Tesileem |
| Contributors | Chemistry, Merola, Joseph S., Hanson, Brian E., Dillard, John G., Tanko, James M., Gibson, Harry W. |
| Publisher | Virginia Tech |
| Source Sets | Virginia Tech Theses and Dissertation |
| Language | English |
| Detected Language | English |
| Type | Dissertation, Text |
| Format | xi, 229 leaves, BTD, application/pdf, application/pdf |
| Rights | In Copyright, http://rightsstatements.org/vocab/InC/1.0/ |
| Relation | OCLC# 24990638, LD5655.V856_1991.L3685.pdf |
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