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garry oak - dmg


Research in the Rosenberg group
We have focused on organophosphorus and organosilicon chemistry, with emphasis on homogeneous catalysis using transition metal complexes, mechanistic aspects of P-H and Si-H activation, catalytic hydrophosphination and phosphine dehydrcopoupling, and the synthesis of functionalized oligo- and polysilanes.

Metal-mediated P-C & P-P bond formation
We develop metal catalysts for the efficient, selective preparation of phosphines, which play an important role in fine chemicals synthesis. We studied the participation of highly reactive terminal phosphido complexes of ruthenium in addition and substitution reactions of the P-H bond in secondary phosphines. This Ru system allowed us to probe "outer-sphere" mechanisms of catalytic hydrophosphination in great detail, identifying critical features for the design of more active catalysts. A "next generation" catalyst based on Co shows unusually broad phosphine substrate scope in hydrophosphination and also catalyzes the dehydrogenative coupling of primary and secondary phosphines, apparently via a new, metal-ligand cooperative P-H activation step. Our recent investigation of the possible role of electrophilic Mo phosphenium complexes in P-H activation chemistry has introduced umpolung into both hydrophosphination and phosphine dehydrocoupling, widening unsaturated substrate scope in the former and providing high, room temperature activity in the latter.


Synthetic routes to functionalized oligosilanes
Methods abound for the construction of organic molecules containing new C-C bonds, but synthetic strategies for incorporating Si-Si bonds are not nearly so well established. We can use metal catalysts to make organosilicon reagents of variable chain length, and then selectively incorporate new side chains via residual Si-H bonds using a Lewis acidic borane catalyst. We have explored the scope of these strategies in the production of new reagents and polymers based on silicon. Recently we also discovered a new thermolytic method for converting linear polysilanes to novel polysilyne materials.



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