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Helical dinuclear 3d metal complexes with bis(bidentate) [S,N] ligands: synthesis, structural and computational studies

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posted on 2024-10-28, 16:51 authored by Jamie Allen, Jörg Saßmannshausen, Kuldip Singh, Sandy KilpatrickSandy Kilpatrick

A diprotic bis(β-thioketoimine) ligand precursor featuring a flexible 4,4′-methylbis(aniline) linker, H22, was synthesised via treatment of the corresponding bis(β-ketoimine) with Lawesson's reagent. Lithiation of H22 and coordination with one equivalent of d-block metal(II) chlorides MCl2(THF)x (M = Fe, Co and Zn) yielded a corresponding series of homoleptic dinuclear complexes, [M2(μ-2)2]. X-ray diffraction analysis reveals a tetrahedral geometry for the two metals and a double-stranded helicate structure arising from inter-strand face-face π-stacking. These interactions create a helical ‘twist’ of ca. 70°. Utilising a bulky mononucleating β-thioketoiminate ligand, [3]−, the analogous series of homoleptic monometallic complexes, [M(3)2] (M = Fe, Co and Zn), were prepared and characterised by spectroscopic and analytical techniques. A comprehensive DFT study of all complexes reveals a stronger M–S bonding compared to M–N due to a higher degree of covalency. Solution magnetic studies and natural bonding orbital calculations on the mono- and dinuclear iron and cobalt complexes are consistent with high-spin tetrahedral Fe(II) and Co(II) centres, and cyclic voltammetry reveals both oxidation and reduction processes are accessible.

History

Author affiliation

College of Science & Engineering Chemistry

Version

  • VoR (Version of Record)

Published in

Dalton Transactions

Publisher

Royal Society of Chemistry (RSC)

issn

1477-9226

eissn

1477-9234

Copyright date

2024

Available date

2024-10-28

Language

en

Deposited by

Dr Sandy Kilpatrick

Deposit date

2024-10-14

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