Issue 13, 2011

Non-oxo vanadium(iv) alkoxide chemistry: solid state structures, aggregation equilibria and thermochromic behaviour in solution

Abstract

The reversible thermochromic behaviour of homoleptic [{V(OR)4}n] complexes in solution [R = Pri (product I), Bus (Bs), Nep (N) and Cy (C)] is accounted for the existence of an aggregation equilibrium involving dimeric and monomeric species in which vanadium(IV) is respectively five- and four-coordinate. Bulky R groups such as But and Pet (tert-pentoxide) prevent aggregation and therefore give rise to exclusively mononuclear compounds (Bt and Pt, respectively) that are not thermochromic. The complexes and their temperature-dependent interconversion were characterised by single crystal X-ray diffractometry, magnetic susceptibility measurements and electronic, FTIR and EPR spectroscopies in a wide temperature range. Equilibrium constants and enthalpy and entropy changes for the dimerization reactions have been determined and compared with literature data.

Graphical abstract: Non-oxo vanadium(iv) alkoxide chemistry: solid state structures, aggregation equilibria and thermochromic behaviour in solution

Supplementary files

Article information

Article type
Paper
Submitted
06 Nov 2010
Accepted
05 Jan 2011
First published
23 Feb 2011

Dalton Trans., 2011,40, 3198-3210

Non-oxo vanadium(IV) alkoxide chemistry: solid state structures, aggregation equilibria and thermochromic behaviour in solution

K. C. M. Westrup, T. Gregório, D. Stinghen, D. M. Reis, P. B. Hitchcock, R. R. Ribeiro, A. Barison, D. F. Back, E. L. de Sá, G. G. Nunes and J. F. Soares, Dalton Trans., 2011, 40, 3198 DOI: 10.1039/C0DT01547D

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