Investigation of the Steric and Electronic Properties of 3-Iminophosphine Ligands in Chelated Palladium Allyl Complexes for Use in the Regioselective Hydroamination of Allenes

A series of (3-iminophosphine)allylpalladium triflate complexes varying in both steric and electronic features was isolated and characterized. The propensity of the complexes in this series to regioselectively catalyze the hydroamination of 3-methyl-1,2-butadiene with aryl amines to form solely the kinetic product at room temperature was studied by observing conversion to products via NMR spectroscopy. An understanding of the importance of these 3-iminophosphine ligand features guides the rational design of future catalysts. The 3-iminophosphine ligand composed of di-tert-butyl phosphine, cyclobutene backbone, and tert-butyl imine provided the most active palladium catalyst for this hydroamination when compared to the other complexes in the collection. Larger alicyclic backbone sizes decrease catalytic activity, as does steric hindrance at the imine substituent group. Tertiary aliphatic groups on the phosphorus are necessary for effective catalysis, as primary and secondary aliphatics and aromatic groups also decrease the catalytic activity. Highly basic imine moieties were also shown to decrease catalytic activity.

Name thesis:degree_name

Master of Science

Level thesis:degree_level

masters

Discipline thesis:degree_discipline

Chemistry

Grantor dc:publisher

University of Toledo

Year dc:date

2013

Author dc:creator

• Zingales, Nicholas C.

Contributors dc:contributor

• Schmidt, Joseph

• Chemistry
• hydroamination
• 3-iminophosphine
• palladium
• intermolecular, anilines
• allenes

Statement dc:rights

• unrestricted
• This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.

Language dc:language

English

Repository record dc:identifier

http://rave.ohiolink.edu/etdc/view?acc_num=toledo1356544579

OAI identifier oai:identifier

oai:etd.ohiolink.edu:toledo1356544579