Wide bite angle phosphines: Synthesis, structure and catalysis

CHED 266

Robert J. Gilliard, rgillia@clemson.edu1, Brad P. Morgan, bradm@clemson.edu1, and Rhett C. Smith, rhett@clemson.edu2. (1) Department of Chemistry, Clemson University, 479 Hunter Labs, Clemson, SC 29634, (2) Department of Chemistry, Center for Optical Materials Science and Engineering Technologies (COMSET), Clemson University, 479 Hunter Labs, Clemson, SC 29634
Bidentate diphosphine ligands have found extensive use in industrially-important catalytic processes. The P–M–P angle (bite angle) afforded by such ligands has a profound impact on the activity of the complexes they support in catalytic processes, and on the regioselectivity of products. The current study focuses on wide bite angle (>120 deg.) diphosphine and diphosphinite ligands and their use in palladium and rhodium catalyzed C-C bond-forming reactions (Suzuki and Heck type coupling and hydroformylation, for example). The facile synthesis of a diverse family of ligands built upon a m-terphenyl scaffold has been accomplished utilizing a common starting material. X-ray crystallographic structure determination and semiempirical calculations on complexes of these ligands allow the characterization of their bite angles. These data, coupled with results from catalytic reactions, have elucidated trends in the bite angle effect.
 

Undergraduate Research Poster Session
2:30 PM-4:30 PM, Monday, August 20, 2007 BCEC -- Exhibit Hall - B2, Poster

Division of Chemical Education

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007