Abstract
Oxidation of the nominally all-ferrous hexanuclear cluster ((H)L)(2)Fe(6) with six equivalents of ferrocenium in the presence of bromide ions results in a six-electron oxidation of the Fe(6) core to afford the nominally all-ferric cluster ((H)L)(2)Fe(6)Br(6). The hexabromide cluster is also structurally characterized in a 4+ core oxidation state. A structural comparison of these two clusters provides an insight into the Fe(6) core electronic structure.
Highlights
We recently reported the synthesis of a hexaamine ligand, HLH6, that, upon deprotonation, readily binds three metal ions in a vicinal trigonal planar arrangement.[5]
We report the preparation of the nominally all-ferric cluster (HL)2Fe6Br6 (1), which is cleanly isolated via a six-electron oxidation of the all-ferrous (HL)2Fe6 by the mild oxidant ferrocenium ion, in the presence of bromide ions
The zero-field 57Fe Mossbauer spectrum of 1, obtained for a powder sample at 100 K, displays a single, symmetric quadrupole doublet with an isomer shift of d = 0.37 mm sÀ1 and a quadrupole splitting of |DEQ| = 2.78 mm sÀ1. These values are in close agreement with those obtained for the related short-lived cluster [(HL)2Fe6(NCMe)6]6+, which features an [(HL)2Fe6]6+ core (d = 0.37 mm sÀ1, |DEQ| = 2.60 mm sÀ1).[6]
Summary
Expanded redox accessibility via ligand substitution in an octahedral Fe6Br6 cluster “Expanded Redox Accessibility via Ligand Substitution in an Octahedral Fe6Br6 Cluster.” Chemical Communications 47, no. T. David Harris, Qinliang Zhao, Raul Hernandez Sanchez and Theodore A.
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