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

被引：22

作者：

Supej, Michael J. ^{[1
]}

Volkov, Alexander ^{[1
]}

Darko, Louisa ^{[1
]}

West, Ryan A. ^{[2
]}

Darmon, Jonathan M. ^{[3
]}

Schulz, Charles E.

Wheeler, Kraig A. ^{[4
]}

Hoyt, Helen M. ^{[1
]}

机构：

[1] Knox Coll, Dept Chem, 2 E South St, Galesburg, IL 61401 USA

[2] Knox Coll, Dept Phys, 2 E South St, Galesburg, IL 61401 USA

[3] Pacific NW Natl Lab, Ctr Mol Electrocatalysis, Div Phys Sci, POB 999,K2-57, Richland, WA 99352 USA

[4] Eastern Illinois Univ, Dept Chem, Charleston, IL 61920 USA

来源：

POLYHEDRON | 2016年 / 114卷

基金：

美国国家科学基金会;

关键词：

Iron; alpha-Diimine; Hydrosilylation; Catalysis; Bis(imino)acenaphthene; LIGAND COPPER(II) COMPLEXES; ZETA VALENCE QUALITY; AUXILIARY BASIS-SETS; GAUSSIAN-BASIS SETS; DIRADICAL CHARACTER; NICKEL-COMPLEXES; HYBRID DFT; ATOMS LI; APPROXIMATE; POLYMERIZATION;

D O I：

10.1016/j.poly.2016.02.020

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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. (C) 2016 Elsevier Ltd. All rights reserved.

引用

页码：403 / 414

页数：12

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