Aryl-substituted BIAN complexes of iron dibromide: Synthesis, X-ray and electronic structure, and catalytic hydrosilylation activity

作者：Supej Michael J; Volkov Alexander; Darko Louisa; West Ryan A; Darmon Jonathan M; Schulz Charles E; Wheeler Kraig A; Hoyt Helen M^*

来源：Polyhedron, 2016, 114: 403-414.

DOI：10.1016/j.poly.2016.02.020

• Iron
• alpha-Diimine
• Hydrosilylation
• Catalysis
• Bis(imino)acenaphthene

Anhydrous iron dibromide complexes bearing bidentate alpha-diimine ligands N-Ar=C(Me) (Me)C=N-Ar and (Ar)BIAN (BIAN = bis(imino)acenaphthene; Ar = dpp and Mes; dpp = 2,6-diisopropylphenyl; Mes = 2,4,6-trimethylphenyl) have been prepared, and characterized by H-1 NMR spectroscopy. The aryl-substituted BIAN complexes were structurally characterized by single-crystal X-ray diffraction, and their metrical parameters are consistent with a redox-innocent chelating ligand. A high-spin iron(II) electronic structure description for the ArBIAN iron complexes is supported by Mossbauer spectroscopy, solution state magnetic measurements, and quantum-chemical calculations. Upon reduction, the iron complexes promote catalytic hydrosilylation of 1-hexene with phenylsilane at 22 degrees C. Under optimized conditions, 1 mol% of the (dPP)BIANFeBr(2) precatalyst was activated in situ to produce 1-hexylphenylsilane in high yield from a 1:1 ratio of 1-hexene:PhSiH3 in solvent-free conditions at 22 degrees C in 24 h.

• 出版日期2016-8-16