Intermediacy of radicals in rearrangement and decomposition of metal-alkyl species: Relevance to metal-mediated polymerization of polar vinyl monomers

POLY 330

Megan L Nagel, m-nagel@bethel.edu, Department of Chemistry, Bethel University, 3900 Bethel Drive, St. Paul, MN 55112 and Ayusman Sen, asen@chem.psu.edu, Department of Chemistry, The Pennsylvania State University, 104 Chemistry Building, University Park, PA 16802.
The neutral compound [2,3-bis(2,6-diisopropylphenylimino)butane]Pd(CH2CH2CH2CO2Me)(X) (X = Cl, Br) undergoes "reverse" chain walking to form [2,3-bis(2,6-diisopropylphenylimino)butane]Pd(CH(CO2Me)CH2CH3)(X) through a conventional -hydrogen elimination/readdition pathway. However, reversible Pd-alkyl bond homolysis occurs for both alkyl complexes, and the resultant radicals can initiate the polymerization of acrylates. Varying the ligand to PR3 (R = Me, Ph, Cy) effects the preferred pathway of decomposition.
 

General Papers and Segmented Block Copolymers
6:00 PM-8:00 PM, Tuesday, March 27, 2007 Hyatt Regency Chicago -- Riverside Center, Poster

Division of Polymer Chemistry

The 233rd ACS National Meeting, Chicago, IL, March 25-29, 2007