Synthesis and reactivity of structurally unusual divalent (PNP) palladium complexes and catalytic carbon-carbon coupling by pincer ligated rhodium

This dissertation explored the chemistry of transition metals supported by diarylamido based PNP pincer ligands and has focused on the chemistry of PNP ligated Pd complexes and the catalytic activity of pincer ligated rhodium complexes.;The synthesis and substitution of the PNP ligands was discussed in Chapter 2 along with the preparation of (PNP)PdX complexes. In Chapter 3 a number of (PNP)Pd alkyl and alkoxy complexes were synthesized. The alkyl complexes were shown to be very stable towards b-hydrogen elimination (BHE), a typical decomposition pathway for late metal alkyl complexes. The stability of these complexes is due to the strong binding of the ligand which, in turn, does not dissociate a phosphine opening up a coordination site needed for BHE to occur. Surprisingly the ethoxide complex showed increased BHE activity with an increase in the concentration of ethanol. A non-classical mechanism for BHE was proposed.