Iron precatalysts bearing α-diimine ligands have been shown to have high catalytic activity in hydrosilylation reactions. These precatalysts typically exist as dihalides, such as dppBIANFeBr2 (dpp = 2,6-diisopropylphenyl, BIAN = Bis(imino)acenaphthene), which must be reduced in situ prior to productive catalysis. While nearly quantitative hydrosilylation yields can be achieved at low catalyst loading and mild conditions with dpp-subsitution on the BIAN ligand, other precatalyst ligand substituents provide significantly lower yields. To determine whether these results are additionally impacted by the in situ reduction step as well as the structure of the active catalyst, the reduced catalysts must be isolated and hydrosilylation yields explored. The electronic and magnetic properties of the active catalysts should also be investigated. Toward this goal, reducing agents were added to the dihalide precatalysts in the presence of coordinating ligands such as cyclooctadiene, toluene, or naphthalene. Ongoing work involves characterizing these reduced species and using these reduced adducts as a starting point for hydrosilylation to compare with in situ reduction yields for the corresponding dihalide precatalysts.

Toward the isolation of reduced iron hydrosilylation catalysts

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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