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

Dr. Christopher C. Cummins of the Massachusetts Institute of Technology will carry out fundamental synthetic chemistry explorations involving d-block and p-block elements. Strained, phosphorus-rich organic molecules will be a special focus of interest. The fundamental significance of the work rests in delivering synthetic access to new groupings of atoms to permit mapping of the consequent reactivity patterns and physical properties. Possible benefits of the project to society will be in the development of methods for the on-demand generation of new kinds of reactive intermediates having synthetic applications to molecules of interest in pharmaceutical chemistry or materials science. The research fits into the NSF Priority Area of Advanced Manufacturing because molecules capable of undergoing low-temperature fragmentation and conversion to extended solids can deliver access to metastable phases inaccessible by conventional synthetic methods. Scientific broader impacts include spectroscopic characterization of new potential interstellar molecules to enable their possible identification by astrochemists. Educational broader impacts will include the professional development of graduate and undergraduate student researchers. The research team of Dr. Cummins will seek to improve the synthesis and characterization procedures for triphosphatetrahedrane, a simple molecule composed of the biogenic elements hydrogen, carbon, and phosphorus. This strained molecule is metastable, converting to a polymeric form that is to be subjected to materials physical analysis. Its electronic structure is of interest in that it may be construed as a methine-doped allotrope of elemental phosphorus. While continuing to improve synthetic methods and applications of diazoborane compounds, the dinitrogen group transfer methodology devised for their synthesis will, if possible, be extended to other main group elements, particularly silicon and phosphorus. To facilitate the synthetic chemistry, simpler to synthesize analogs of Carpino’s hydrazine will be investigated. In a similar context, efforts to stabilize molecular boron nitride will be undertaken. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.