projects in the
projects focus on organosilicon and organophosphorus chemistry, with
emphasis on homogeneous catalysis using transition metal complexes,
mechanistic aspects of Si-H and P-H activation, and structure/property
relationships in oligo- and polysilanes.
|Metal-mediated P-C bond formation
We're interested in developing metal
catalysts for the efficient, stereoselective preparation of chiral
phosphines, which play an important role in fine chemicals synthesis.
We are examining the participation of some highly reactive terminal
phosphido complexes of ruthenium in addition and substitution reactions
of the P-H bond in secondary phosphines.
|Synthetic routes to functionalized
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're
exploring the scope of these strategies in the production of new
reagents and polymers based on silicon.
|Catalytic silane dehydrocoupling
The Rh-catalyzed formation of Si-Si bonds
and secondary silanes allows us to make oligosilanes containing
reactive Si-H bonds. However, the mechanism of this dehydrogenative
coupling by late metal catalysts remains poorly understood, so we are
using NMR and (in collaboration with the McIndoe group) electrospray
MS to learn more and develop more active catalysts.