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Issue 10, 2014
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Gauging metal Lewis basicity of zerovalent iron complexes via metal-only Lewis pairs

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Abstract

A range of pentacoordinate iron complexes of the form [Fe(CO)5−nLn] (L = neutral donor, n = 0–2) were treated with gallium chloride or bromide, leading to hexacoordinate metal-only Lewis pairs (MOLPs) of the form [Ln(OC)5−nFe → GaX3] (X = Cl, Br). These complexes were used to gauge the Lewis basicity of the pentacoordinate iron precursors through comparison of their experimentally- and computationally-derived Fe–Ga distances and the degree of pyramidalization at the Ga center. The data indicate that consecutive replacement of CO groups with donor ligands increases the Lewis basicity of [Fe(CO)5−nLn] complexes, with the largest effect seen upon going from n = 0 to n = 1. While the Lewis basicity differences are clear between tri-, tetra- and pentacarbonyl complexes, the difference between the ligands within each group is less clear. A series of transfer experiments were also performed, in which the GaCl3 was transferred consecutively to Fe complexes with increasing numbers of donor ligands.

Graphical abstract: Gauging metal Lewis basicity of zerovalent iron complexes via metal-only Lewis pairs

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Publication details

The article was received on 26 May 2014, accepted on 14 Jul 2014 and first published on 15 Jul 2014


Article type: Edge Article
DOI: 10.1039/C4SC01539H
Citation: Chem. Sci., 2014,5, 4099-4104
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    Gauging metal Lewis basicity of zerovalent iron complexes via metal-only Lewis pairs

    H. Braunschweig, R. D. Dewhurst, F. Hupp, C. Kaufmann, A. K. Phukan, C. Schneider and Q. Ye, Chem. Sci., 2014, 5, 4099
    DOI: 10.1039/C4SC01539H

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