Phosphine-Borane Dehydrocoupling: The Synthesis of Tailored New Materials through Mechanistic Studies of Catalytic Processes.

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Transition-metal-catalysed reactions the make or break C-C, C-H or C-X bonds are cornerstone in the synthesis of commodity/feedstock chemicals and fine-chemicals. The elucidation of mechanism for such processes has led to major breakthroughs of fundamental, commercial and societal importance (e.g. routes to new pharmaceuticals, polymer synthesis, the synthesis of new materials with exciting properties, more efficient and greener ways to construct new molecules). By contrast the development of analogous catalytic routes to prepare bonds between main-group elements is still nascent. This gap in knowledge/technology is remarkable given the potential that such routes would have for the synthesis of novel polymers, new materials, electronic devices as well as new organic methodology and the synthesis of biologically active molecules. Recently there has been intense interest in catalytic dehydrocoupling strategies for group 13/15 materials, prototypically H3B-NRRH and H3B-PRRH (R = alkyl, aryl, H) that are precursors for new hydrogen-delivery systems or novel polymeric materials. Group 13/15 polymers are relatively unexplored, yet are important as analogues of polymeric all-carbon systems that could potentially have technologically useful thermophysical, pre-ceramic and other useful materials properties. Remarkably, lacking is a unified mechanistic approach to the design of catalyst systems that allows for the bespoke production of such materials. In this project we will provide full mechanistic details for dehydrocoupling and use this knowledge to design, develop and implement catalyst systems that will generate new phosphine-borane (P/B) materials. Our goal is the targeted synthesis of well-defined novel monomeric, oligomeric and polymeric phosphine-boranes that will have significant potential for future technological applications.