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Research projects in the Rosenberg group
Our current projects focus 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 the synthesis of
functionalized oligo- and polysilanes.
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Metal-mediated
P-C bond formation
We're interested in developing
metal catalysts for the efficient, selective
preparation of phosphines, which play an
important role in fine chemicals synthesis. We
have examined the participation of some highly
reactive terminal phosphido complexes of
ruthenium in addition and substitution reactions
of the P-H bond in secondary phosphines. This Ru
system has also allowed us to probe
"outer-sphere" mechanisms of catalytic
hydrophosphination in great detail, identifying
critical features for the design of more active
catalysts. Recently we
have begun to explore the potential of Co and Mo
complexes in new types of P-H activation
chemistry, with the goal of widening substrate
scope in catalytic hydrophosphination
chemistry.
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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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