Oxidative addition of N-H and O-H bonds to iridium: developing active catalysts for N-H and O-H additions to unsaturates

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.

Name thesis:degree_name

Ph. D.

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemistry

Department dc:contributor.department

Chemistry

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

1991

Author dc:creator

• Lapido, Folami Tesileem

Chair dc:contributor.committeechair

• Merola, Joseph S.

Committee members dc:contributor.committeemember

• Hanson, Brian E.
• Dillard, John G.
• Tanko, James M.
• Gibson, Harry W.

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Language dc:language.iso

en

Dc Identifier Other

etd-10132005-152537

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/39829