International Collaboration in Chemistry: Carbenes as Stabilizing and Activating Agents in Boron, Carbon and Phosphorus Chemistry

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This International Collaborations in Chemistry award funded by the Inorganic, Bioinorganic, and Organometallic Chemistry Program and the Office of International Science and Engineering supports work by Professor Guy Bertrand of the University of California at Riverside to carry out fundamental/basic studies on the use of stable carbenes. These novel carbenes are used for stabilizing highly reactive species and for activating stable molecules. The synthesis of carbene-stabilized monoatomic and diatomic carbon(0) compounds is being investigated. These compounds are of considerable importance in biology and in synthetic chemistry. Synthetic cycles using carbenes to activate P4 and the subsequent addition of organic fragments to the ensuing highly reactive mono- and diatomic phosphorus species are being developed. Indeed, processes using white phosphorus, but avoiding chlorine, are highly desirable to meet the growing demand for phosphorus derivatives under increasingly stringent environmental regulations. The carbene-induced de-oligomerization of BNH containing polymers also under investigation. The greatest technical barrier for a practical application of ammonia borane as a hydrogen-storage material for fuel-cell-powered vehicles lies in the discovery of energy-efficient regeneration routes from the polymers that are formed in the dehydrogenation process. Calculations to accurately describe these novel compounds are being performed by Professor Bertrand's German collaborator, Professor Gernot Frenking of Phillipps-Universitaet Marburg. This German work is separatately supported by the Deutsche Forschungsgemeinschaft (DFG). This project is at the interfaces between organic, inorganic, and physical chemistry and is well-suited for the multidisciplinary education of graduate coworkers. The graduate students of the U.S. and German groups involved in this collaborative effort have the opportunity to learn both computational and experimental techniques through reciprocal visits of three months. This project addresses several issues that are of critical importance for society, such as the study of substances with potential biological applications (para-benzynes), the environmentally friendly synthesis of bulk chemicals (phosphorus derivatives), and the hydrogen economy (ammoniaborane).