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

Journal Article · Tue Aug 16 04:00:00 EDT 2016 · Polyhedron

DOI:https://doi.org/10.1016/j.poly.2016.02.020· OSTI ID:1700666

Supej, Michael J. ^[1]; Volkov, Alexander ^[1]; Darko, Louisa ^[1]; West, Ryan A. ^[1]; Darmon, Jonathan M. ^[2]; Schulz, Charles E. ^[1]; Wheeler, Kraig A. ^[3]; Hoyt, Helen M. ^[1]

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1. Knox College
2. BATTELLE (PACIFIC NW LAB)
3. Eastern Illinois University

Anhydrous iron dibromide complexes bearing bidentate a-diimine ligands ArN@C(Me)A(Me)C@NAr and ArBIAN (BIAN = bis(imino)acenaphthene; Ar = dpp and Mes; dpp = 2,6-diisopropylphenyl; Mes = 2,4,6-trimethylphenyl) have been prepared and characterized by 1H 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 Mössbauer spectroscopy, solution state magnetic measurements, and quantum-chemical calculations. Upon reduction, the iron complexes promote catalytic hydrosilylation of 1-hexene with phenylsilane at 22 _C. Under optimized conditions, 1 mol% of the dppBIANFeBr2 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 _C in 24 h.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1700666
• Report Number(s): PNNL-SA-120427
• Journal Information: Polyhedron, Journal Name: Polyhedron Vol. 114
• Country of Publication: United States
• Language: English