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Issue 48, 2014
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Metal effects on ligand non-innocence in Group 5 complexes of the redox-active [ONO] pincer ligand

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Abstract

Isostructural vanadium, niobium and tantalum complexes of bis(3,5-di-tert-butyl-2-phenol)amine ([ONO]H3), were prepared and characterized to evaluate the impact of the metal ion on redox-activity of the ligand platform. New vanadium and niobium complexes with the general formula, [ONO]MCl2L (M = V, L = THF, 1-V; M = Nb, L = Et2O, 1-Nb) were prepared and structurally analysed by X-ray crystallography. The solid-state structures indicate that the niobium derivative is electronically analogous to the tantalum analog 1-Ta, containing a reduced (ONO) ligand and a niobium(V) metal ion, [ONOcat]NbVCl2(OEt2); whereas, the vanadium derivative is best described as a vanadium(IV) complex, [ONOsq]VIVCl2(THF). One-electron oxidation was carried out on all three metal complexes to afford [ONO]MCl3 derivatives (3-V, 3-Nb, 3-Ta). For all three derivatives, oxidation occurs at the (ONO) ligand. In the cases of niobium and tantalum, electronically similar complexes characterized as [ONOsq]MVCl3 were obtained and for vanadium, ligand-based oxidation led to the formation of a complex best described as [ONOq]VIVCl3. All complexes were characterized by spectroscopic and electrochemical methods. DFT and TD-DFT calculations were used to probe the electronic structure of the complexes and help verify the different electronic structures stemming from changes to the coordinated metal ion.

Graphical abstract: Metal effects on ligand non-innocence in Group 5 complexes of the redox-active [ONO] pincer ligand

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Supplementary files

Article information


Submitted
24 Jul 2014
Accepted
13 Oct 2014
First published
29 Oct 2014

Dalton Trans., 2014,43, 17991-18000
Article type
Paper

Metal effects on ligand non-innocence in Group 5 complexes of the redox-active [ONO] pincer ligand

S. Hananouchi, B. T. Krull, J. W. Ziller, F. Furche and A. F. Heyduk, Dalton Trans., 2014, 43, 17991
DOI: 10.1039/C4DT02259A

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