Hydrocarbons from petroleum and natural gas supply over 90% of the carbon feedstock used in industry. Selectively activating and functionalizing C-H bonds of hydrocarbons to form more valuable products is challenging. One such desired transformation is the oxidation of hydrocarbons using molecular oxygen as the oxidant. Oxygen is an ideal oxidant on account of it being abundant, cheap, and environmentally benign. To develop systems that use O2 we need more understanding on how oxygen reacts with organometallic complexes. This talk will discuss the reactivity of PNP (PNP = 1,3-(CH2PtBu2)2C5H3N) and PCP (PCP = [1,3-(CH2PtBu2)2C6H3]-) PdII-Me complexes with molecular oxygen. In particular, the difference in reactivity between each ligand system will be explored. For example, O2 reacts at the pincer arm in the PNP system, whereas in the PCP system O2 reacts at the metal center resulting in oxidation of the Pd-Me group. Products have been characterized by NMR spectroscopy and X-ray crystallography. Isotopic labeling studies, radical initiators, and varied solvent investigations provide insight into the mechanisms of these unusual reactions of late metal alkyls with molecular oxygen.

Reactions of pincer-type PdII-Me complexes with molecular oxygen

251st National Meeting (2016)

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