Fundamental reactivity of PtII/PtIV redox couple relevant to oxidative alkane C-H bond functionalization with O2 as direct oxidant

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With this award, the Chemical Synthesis Program of the Chemistry Division is funding Professor Andrei N. Vedernikov of the University of Maryland to develop new catalysts for converting compounds typically abundant in natural gas, i.e unreactive hydrocarbons into functionalized compounds with added value. Importantly, this 'green' project proposes to use oxygen from the air as the only consumable reagent for the desired oxidative transformations. To accomplish the goal, computational design is combined with experimental study of the reactions involved. To enhance the chances for success the project includes collaboration with the theoretical computational group of Professor William A. Goddard, III from Caltech. The broader impacts include the training of students via the ACS Project SEED Program from area high schools through participation in this research.This project aims at a detailed mechanistic understanding of how facially chelating ligands control reactivity of a Pt center in alkane C-H bond activation. These studies follow on earlier work in Professor Vedernikov's group on Pt(II)species that mediate aerobic functionalization of C-H bonds. Several series of novel Pt(II) complexes are being developed, including sulfonated CNN pincer complexes and macrocyclic pyridinophane complexes. This work includes DFT (Density Functional Theory)-driven catalyst discovery and detailed mechanistic characterization of new systems by means of kinetics, isotopic labeling experiments and DFT calculations. If successful, some of the new systems may serve as efficient catalysts for partial aerobic oxidation of methane and higher alkanes.