In the recent years our group's research has been focused on the diarylamido-based PNP pincer ligands in application to a variety of transition metal centers. The rigidly meridional, tridentate, anionic PNP ligand is ideally set up for forming square planar (PNP)M-X complexes. We have exploited this trait in the chemistry of palladium. We will discuss some surprising findings in the chemistry of the Pd alkyl complexes (PNP)Pd-R. In contrast to most Pd(II) alkyls, these compounds are thermally inert toward β-hydrogen elimination. We ascribe this to the ability of the PNP ligand to bind to the metal rigidly, preventing formation of empty coordination sites that are necessary for β-hydrogen elimination to proceed. On the other hand, many (PNP)Pd-R compounds are sensitive to sunlight (a serendipitous discovery!) and, hence, not surprisingly, to the UV-radiation of a 350 nm lamp. The photolytic decomposition cleanly leads to a Pd(I) product. Characterization of the reported compounds by NMR, X-ray diffraction, and other techniques will be discussed with a special emphasis on the utility of the 19F NMR.
Web Page: people.brandeis.edu/~ozerov/
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