SusChEM: Catalytic Element-Element Bond Formation: Selectivity and New Catalysis with a Movement Toward Sustainability

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The Chemical Catalysis Program of the NSF Division of Chemistry supports the research efforts of Professor Rory Waterman of the University of Vermont in the discovery and understanding of catalytic reactions that form bonds between main group elements. Efforts under this award focus on new or improved catalytic reactivity for transformations that form bonds to phosphorus (P). Catalytic dehydrocoupling of phosphines is applied toward the synthesis of novel materials featuring P-P sigma-bonds. Hydrophosphination catalysts, particularly those with primary phosphine substrates, are applied in the preparation of new transition-metal ligands for other catalytic reactions. The unique phosphaalkene synthesis discovered by Prof. Waterman is used in the catalytic preparation of unsaturated phosphorus products. An expansion of alpha elimination catalysis using phosphines as substrates is sought as well. Investigation of these transformations is geared toward expansion to other elements, and provides a venue to train university students as well as outreach opportunities to include high school students in research.Catalytic syntheses of molecules containing heavier main group elements such as phosphorus or silicon continue to lag substantially behind organic analogs. The disparity in the ease of transformations has slowed the development of main group materials and resulted in high costs for current main group-containing products in terms of both the energy required and the waste produced. These main group-containing molecules are essential components to industrial and consumer products. Some evidence for this comes from the $13 billion silicone industry alone. Research under this award seeks to provide new feedstocks, synthetic methods, materials, or more efficient syntheses that could improve such enterprises. Phosphorus is a finite resource. The discovery of efficient syntheses may help to preserve phosphorus resources. This research is identified as part of a sustainability chemical portfolio because it is identifying transition metal catalysts that can replace phosphorus in certain applications, to protect our phosphorus-containing resources. Students involved in this research are training to contribute to chemical industry and are also learning to use catalysis for sustainability.