Mechanism of formation of iron(ii) complexes with pentadentate ligandsvia C–C bond formation between trans-[Fe(2,4-bis(2-pyridylmethylimino)pentane)(MeCN)2][ClO4]2·MeCN and various nitriles

Dalton Transactions Pub Date: 2005-02-07 DOI: 10.1039/B414207A

Abstract

The order of relative reactivity of nitriles for the formation of Fe(II) complexes (2s) with 3-(1-alkyl(or aryl)methyl)-1-imino-2,4-bis(2-pyridylmethylimine) (L2s) from that with 2,4-bis(2-pyridylmethylimono)pentane (L1), trans-[FeL1(MeCN)2][ClO4]2·MeCN (1), and various nitriles has been determined based on the following order: C6F5CN > 3,4-difluorobenzonitrile > 4-fluorobenzonitrile > C6H5CN > C6H5CH2CN > C2H5CN > MeCN > Me2CHCN ? Me3CN. An iron(II) complex with L1 in a cis-configuration was prepared as the ternary complex [FeL1(bpy)][ClO4]2·1.5MeNO2·0.5H2O, 3a (bpy = bipyridine). Compounds 2s and 3a undergo enantiomeric interconversion with an activation energy of ca. 60 kJ mol?1.

Graphical abstract: Mechanism of formation of iron(ii) complexes with pentadentate ligands via C–C bond formation between trans-[Fe(2,4-bis(2-pyridylmethylimino)pentane)(MeCN)2][ClO4]2·MeCN and various nitriles
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