Unexpected structures and reactivity of (PNP)Pd complexes

INOR 381

Claudia M. Fafard1, Chun-Hsing Chen1, Chengyun Guo1, Debashis Adhikari, dadhikar@indiana.edu2, Bruce M. Foxman1, Daniel J. Mindiola, mindiola@indiana.edu2, and Oleg V. Ozerov, ozerov@brandeis.edu1. (1) Department of Chemistry, Brandeis University, MS 015, Brandeis University, 415 South St., Waltham, MA 02454, (2) Department of Chemistry, Indiana University, 800 E. Kirkwood, Bloomington, IN 47405
In recent years our group has focused on the chemistry of various metals containing diarylamine PNP ligands. Pincer ligands have been shown to support unusual structures and reactivities. In studying Pd alkyl complexes, (PNP)PdR, we found these complexes to be thermally stable to β-hydrogen elimination. Surprisingly, they are not photochemically stable. Upon exposure to ambient or UV light, the Pd-C bond is homolytically split and a novel Pd(I)-Pd(I) dimer is formed. Interestingly the PNP ligands do not reorganize and each PNP ligand remains bound to a Pd center in a square planar tridentate fashion resulting in an unsupported Pd-Pd bond. The characterization by NMR and X-ray diffraction will be discussed as well as the reactivity of these Pd(I) dimers.

 

General Organometallic Chemistry
9:00 AM-12:20 PM, Monday, August 20, 2007 BCEC -- 211, Oral

Division of Inorganic Chemistry

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