Issue 12, 2010
From the journal:

New Journal of Chemistry

Synthesis, structural characterisation and bonding in an anionic hexavanadate bearing redox-active ferrocenylgroups at the periphery†

Jiří Schulz,a   Róbert Gyepes,ab   Ivana Císařováa  and  Petr Štěpnička*a  

* Corresponding authors

a Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 12840 Prague, Czech Republic
E-mail: stepnic@natur.cuni.cz
Fax: +420 221 951 253

b J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Dolejškova 3, 18223 Prague 8, Czech Republic

Abstract

Amide FcCONHC(CH2OH)3 (1; Fc = ferrocenyl), prepared from fluorocarbonylferrocene and tris(hydroxymethyl)methylamine, reacts with (Bu4N)3[H3V10O28] in N,N-dimethylacetamide to afford a salt containing a bis(triolato) capped hexavanadate anion bearing two ferrocenyl groups at its periphery, (Bu4N)2[{FcC(O)NHC(CH2O)3}2V6O13] (2). Compounds 1 and 2 were characterised by elemental analysis, spectroscopic methods (IR, NMR, and MS) and by cyclic voltammetry; the crystal structures of 1·1/2CH3CO2Et and (Bu4N)2[{FcC(O)NHC(CH2O)3}2V6O13]·2Me2NCHO were determined by X-ray diffraction analysis. Single-point DFT calculations performed for the isolated hexavanadate anion revealed the presence of 3-centre 4-electron (3c4e) O–V–O bonds on the hexavanadate cage, which are responsible for the high energy of the occupied frontier orbitals. The upper eleven occupied molecular orbitals including the HOMO are all delocalized over the hexavanadate cage and, therefore, any electrochemical oxidation can be expected to occur preferentially at the hexavanadate anion without affecting the pendant ferrocene moieties.

Graphical abstract: Synthesis, structural characterisation and bonding in an anionic hexavanadate bearing redox-active ferrocenyl groups at the periphery

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Article information

DOI
https://doi.org/10.1039/C0NJ00421A
Article type
Paper
Submitted
02 Jun 2010
Accepted
18 Jul 2010
First published
23 Aug 2010

New J. Chem., 2010,34, 2749-2756

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Synthesis, structural characterisation and bonding in an anionic hexavanadate bearing redox-active ferrocenyl groups at the periphery

J. Schulz, R. Gyepes, I. Císařová and P. Štěpnička, New J. Chem., 2010, 34, 2749 DOI: 10.1039/C0NJ00421A

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