Transition metal terminal oxo complexes are interesting in that they can exist as thermodynamic sinks and are exceedingly rare for late transition metals. Hence, they pose intriguing synthetic challenges. Such complexes have been demonstrated to be reactive intermediates in biological and chemical processes, such as the photocatalytic oxidation of water. Of relevance to such a process are terminal oxo complexes of Pt which, to date, have been nearly impossible to isolate because of their reactivity. Ideally, the CCC-NHC pincer architecture could stabilize these complexes allowing for isolation. Several synthetic approaches will be discussed, which have led to many observations including the isolation of two dimeric Pt(IV) species. Products of these reactions are characterized by 1H, 13C{1H}, and 195Pt NMR spectroscopy and X-ray crystallography. DFT computations have been used to aid in the prediction and identification of oxidation products and intermediates involved in the reaction pathway.

Accessing reactive oxo intermediates: Oxidation of a CCC-NHC-Pt complex

255th National Meeting (2018)

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