The Brookhart group carries out research in the general area of synthetic
and mechanistic organometallic chemistry with particular emphasis
on the application of organometallic complexes in catalysis.
One major thrust is the development of late transition metal
complexes (Ni, Pd, Fe, Co) for olefin polymerization. These non-traditional
catalysts allow synthesis of polymers with unique microstructures,
such as hyperbranched polyethylene and chain-straightened poly(a-olefins).
The functional group tolerance of these late transition metal
systems allows copolymerization of monomers such as methyl acrylate
with nonpolar monomers such as ethylene and propylene. In addition,
new catalysts are also under investigation for living polymerization
systems, as well as the alternating copolymerization of olefins
and CO to yield polyketones. Mechanistic probes of these reactions
employ primarily low temperature IR and NMR spectroscopies and
provide a detailed understanding of catalyst resting states and
relative intermediates.
A second major focus concerns fundamental studies of C-H and C-C
bond activations by transition metal complexes and the incorporation
of these bond activation steps into catalytic cycles. Co, Rh,
and Ru complexes have been developed which catalyze the ortho-alkylation
of aromatic ketones, alkyl aldehyde isomerization, hydroacylation,
and the dehydrogenation of alkoxy silanes to generate silyl enol
ethers. Again, thorough mechanistic studies dictate the development
of second generation catalyst systems. |