New heterodonor phosphine and bipyridine ligands
1University of Oulu, Faculty of Science, Department of Chemistry
|Online Access:||PDF Full Text (PDF, 2.6 MB)|
|Persistent link:|| http://urn.fi/urn:isbn:9514252292
|Publish Date:|| 1999-04-16
|Thesis type:||Doctoral Dissertation
|Defence Note:||Academic Dissertation to be presented with the assent of the Faculty of Science, University of Oulu, for public discussion in Raahensali (Auditorium L 10), on May 28th, 1999, at 12 noon.
Docent Erkki Kolehmainen
Professor Markku Leskelä
Twenty-seven phosphine and six bipyridine ligands were synthesised and characterized. Additionally, a new route to the family of phosphine ligands via o-thioanisyldichlorophosphine was found. The phosphine ligands contain thiomethylphenyl, methoxyphenyl, dimethylaminophenyl, pyridyl, naphthyl and anthracenyl groups, and the bipyridine ligands thiomorpholine and piperidine groups. Metal complexes of 3-pyridyldiphenylphosphine, 6,6'-bis(methylthiomorpholine)-2,2'-bipyridine and 4,4'-dimethyl-6,6'-bis(methylthiomorpholine)-2,2'-bipyridine were prepared.
Ligands and complexes were characterized by ¹H-, ¹³C-, ³¹P- and two-dimensional HSQC-NMR spectroscopy, and crystal structures were determined for the ligands and two of the metal complexes. Tertiary phosphine ligands were prepared for catalytic purposes and tested in hydroformylation reaction at the Helsinki University of Technology and the University of Joensuu. Bipyridine ligands were designed for bimetallic coordination.
The phosphine ligands cover a wide range of electronic and steric properties. The spectroscopic parameters and crystal structures were studied with the purpose of charting trends in the basicities and steric effects of the ligands.
Acta Universitatis Ouluensis. A, Scientiae rerum naturalium
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