Type of Document Master's Thesis Author Merrill, James Malcolm URN etd-01102002-163336 Title Coordination Chemistry of Bis(diphenylphosphino)amine Ligands with Cobalt Carbonyl and the Intermolecular Catalyzed Pauson-Khand Reaction Degree Master of Science Department Chemistry Advisory Committee
Advisor Name Title Hanson, Brian E. Committee Chair Deck, Paul A. Committee Member Dillard, John G. Committee Member Keywords
- phosphine ligands
- homogeneous catalysis
Date of Defense 2001-12-19 Availability unrestricted AbstractBis(diphenylphosphino)amine (PNP) ligands, prepared from (S)-(-)-1-methylbenzyl amine, (-)-cis-myrtanylamine, (S)-(-)-1,1-napthyl(ethyl)amine (PNP1 1a, PNP2 1b, and PNP3 1c respectively) and their cobalt carbonyl complexes are reported. In the absence of alkynes the PNP ligands chelate to the cobalt rather than bridging the two cobalt centers. Although the PNP ligands are chiral the crystal structures are best solved in centrosymmetric space groups with disorder at the chiral carbon with the exception of (PNP3)Co2(CO)6, 2c, which is solved in a non-centrosymmetric space group.
When the PNP ligand chelates to cobalt, as in 2, the compounds show activity for the catalytic Pauson-Khand reaction, whereas when the PNP ligand bridges, as in 3, the reaction precedes stiochiometrically. The use of these chiral ligands has not yet resulted in enantioselective catalytic Pauson-Khand cycloadditions. However, a small 15% e.e. was detected for the stiochiometric Pauson-Khand cycloaddition with 3c as the metal substrate.
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