Recently, we reported that the in situ reduction of iron(II) bromide complexes dppBIANFeBr2 and dppDIFeBr2 (dpp = 2,6-diisopropylphenyl; BIAN = bis(imino)acenaphthene; DI = N=C(Me)-(Me)C=N) with LiCH2SiMe3, followed by subsequent catalytic hydrosilylation of 1-hexene with phenylsilane, demonstrated nearly quantitative yields as determined by 1H NMR spectroscopy. In contrast, less sterically bulky N-substituents of both BIAN and DI ligand backbones, such as 2,4,6-trimethylphenyl and 4-tert-butylphenyl, provided low to moderate hydrosilylation yields under similar conditions. To investigate in more depth the factors responsible for this observed reactivity, a larger series of iron(II) bromide precatalysts bearing N-substituted BIAN and DI ligands has been prepared. Hydrosilylation and electronic structure studies, including Mössbauer spectroscopy and magnetic susceptibility measurements, have been performed to analyze the electronic factors required to promote successful catalysis.

Tuning hydrosilylation of hydrocarbons with substituted alpha-diimine iron(II) bromide precatalysts

255th National Meeting (2018)

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