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Issue 31, 2018
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The modular synthesis of rare earth-transition metal heterobimetallic complexes utilizing a redox-active ligand

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Abstract

We report a robust and modular synthetic route to heterometallic rare earth-transition metal complexes. We have used the redox-active bridging ligand 1,10-phenathroline-5,6-dione (pd), which has selective N,N′ or O,O′ binding sites as the template for this synthetic route. The coordination complexes [Ln(hfac)3(N,N’-pd)] (Ln = Y [1], Gd [2]; hfac = hexafluoroacetylacetonate) were synthesised in high yield. These complexes have been fully characterised using a range of spectroscopic techniques. Solid state molecular structures of 1 and 2 have been determined by X-ray crystallography and display different pd binding modes in coordinating and non-coordinating solvents. Complexes 1 and 2 are unusually highly coloured in coordinating solvents, for example the vis-NIR spectrum of 1 in acetonitrile displays an electronic transition centred at 587 nm with an extinction coefficient consistent with significant charge transfer. The reaction between 1 and 2 and VCp2 or VCpt2 (Cpt = tetramethylcyclopentadienyl) resulted in the isolation of the heterobimetallic complexes, [Ln(hfac)3(N,N′-O,O′-pd)VCp2] (Ln = Y [3], Gd [4]) or [Ln(hfac)3(N,N′-O,O′-pd)VCpt2] (Ln = Y [5], Gd [6]). The solid state molecular structures of 3, 5 and 6 have been determined by X-ray crystallography. The spectroscopic data on 3–6 are consistent with oxidation of V(II) to V(IV) and reduction of pd to pd2− in the heterobimetallic complexes. The spin-Hamiltonian parameters from low temperature X-band EPR spectroscopy of 3 and 5 describe a 2A1 ground state, with a V(IV) centre. DFT calculations on 3 are in good agreement with experimental data and confirm the SOMO as the dx2y2 orbital localised on vanadium.

Graphical abstract: The modular synthesis of rare earth-transition metal heterobimetallic complexes utilizing a redox-active ligand

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Publication details

The article was received on 31 Mar 2018, accepted on 02 Jun 2018 and first published on 06 Jun 2018


Article type: Paper
DOI: 10.1039/C8DT01262H
Citation: Dalton Trans., 2018,47, 10692-10701
  • Open access: Creative Commons BY license
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    The modular synthesis of rare earth-transition metal heterobimetallic complexes utilizing a redox-active ligand

    J. R. Hickson, S. J. Horsewill, C. Bamforth, J. McGuire, C. Wilson, S. Sproules and J. H. Farnaby, Dalton Trans., 2018, 47, 10692
    DOI: 10.1039/C8DT01262H

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