Synthesis of d- and p-Block Element Molecules, Reagents, and Precursors

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In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Christopher Cummins of MIT will develop new methods (recipes) that will enable the production of next-generation electronic materials. Professor Cummins and coworkers are also aiming to optimize and simplify the recipes so they can be broadly adopted and commercialized. The efforts to synthesize value-added compounds directly from elemental phosphorus are relevant to ongoing developments in the chemical industry, a specific example being the Monsanto synthesis of the herbicide glyphosate. Results from gas-phase studies are relevant to the chemical evolution of the cosmos and useful in providing fundamental constants crucial to the detection and identification of species such as cis-diazene in the interstellar medium. In addition, Professor Cummins and his students are actively disseminating the results of their innovative synthetic chemistry via YouTube videos, which serve as an educational resource and help students understand chemical synthesis. They are also engaged in outreach to introduce methods of molecular modeling and concepts of chemical bonding to students at East Boston Public HS.The proposed research explores novel transition-metal complexes and their small-molecule activation chemistry with an emphasis on reactions of molecular nitrogen and phosphorus (N2 and P4) and the generation of metal-ligand multiple bonds. A key direction of the project is the synthesis of molecular precursors to reactive intermediates. In the case of phosphorus, the PI and coworkers have designed reagents capable of undergoing retro [4+2] cyclization reactions to transfer diatomic P2 either in solution or into the gas phase. The same system that functions with release of anthracene as a thermodynamic driving force provides opportunity to study generation of the P2O molecule, with both organic and transition-metal systems being targeted as thermal precursors to PN, HCP, HCAs, vinylidene, and cis-diazene.