The reversible thermochromic behaviour of homoleptic [{V(OR)(4)}(n)] complexes in solution [R = Pr(i) (product I), Bu(s) (B(s)), 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 Bu(t) and Pe(t) (tert-pentoxide) prevent aggregation and therefore give rise to exclusively mononuclear compounds (B(t) and P(t), 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.

Highly stable and crystalline V(2)O(5) nanoparticles with an average diameter of 15 nm have been easily prepared by thermal treatment of a bariandite-like vanadium oxide, V(10)O(24) x 9 H(2)O. Their characterization was carried out by powder X-ray diffractometry (XRD), Fourier transform infrared (FT-IR) and Raman spectroscopies, and transmission electron microscopy (TEM). The fibrous and nanostructured film obtained by electrophoretic deposition of the V(2)O(5) nanoparticles showed good electroactivity when submitted to cyclic voltammetry in an ionic liquid-based electrolyte. The use of this film for the preparation of a nanostructured electrode led to an improvement of about 50% in discharge capacity values when compared with similar electrodes obtained by casting of a V(2)O(5) xerogel.

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Dois complexos contendo vanádio e lítio, [V 6 Li 10 O 8 (ONep) 14 {OSi(Me) 2 (ONep)} 2 ] (1) e [V(ONep) 3 (μ-ONep) 2 Li(thf) 2 ] (2), Nep = neopentila, Me = metila e thf = tetraidrofurano, foram isolados em alto rendimento e caracterizados por diversas técnicas incluindo espectroscopias de ressonância paramagnética eletrônica (RPE, banda X) e ressonância magnética nuclear (RMN) de 29 Si, medidas de susceptibilidade magnética e difratometria de raios X de monocristal. A despeito das condições similares de preparação, os dois produtos apresentam características estruturais admiravelmente distintivas: o complexo binuclear não-oxo 2 é um simples produto de adição de "V(ONep) 4 " e "Li(ONep)(thf) 2 ", enquanto 1 é um agregado de valência mista com 16 centros metálicos. O oxoalcóxido molecular 1 também contém grupos silanolatos, {OSi(Me 2 )(ONep)} − , produzidos por ataque nucleofílico de neopentóxidos à graxa de silicone dissolvida acidentalmente no meio de reação. Ambos os produtos têm aplicações promissoras em síntese orgânica e inorgânica, incluindo a preparação de óxidos mistos pouco comuns contendo vanádio, lítio e/ou silício.Two complexes containing both vanadium and lithium, [V 6 Li 10 O 8 (ONep) 14 {OSi(Me) 2 (ONep)} 2 ] (1) and [V(ONep) 3 (μ-ONep) 2 Li(thf) 2 ] (2), Nep = neopentyl, Me = methyl and thf = tetrahydrofuran, have been isolated in high yield and characterised by a number of techniques including X-band electron paramagnetic resonance (EPR) and 29 Si{ 1 H} nuclear magnetic resonance (NMR) spectroscopies, magnetic susceptibility measurements and single crystal X-ray diffractometry. Despite the similar preparation conditions, the two products present remarkably distinctive structural features: complex 2 is a binuclear adduct of "V(ONep) 4 " and "Li(ONep)(thf) 2 ", while 1 is a mixed-valence, 16-metal aggregate. The large molecular oxoalkoxide 1 also contains silanolate units, {OSi(Me 2 )(ONep)} − , produced by nucleophilic attack of neopentoxide groups on Si-O bonds of silicone grease accidentally dissolved in the reaction media. Both products have promising applications in organic and inorganic synthesis, including the preparation of uncommon V-Li and/or Si containing oxides. Keywords: vanadium(IV), lithium, alkoxide, silicone grease, neopentoxide IntroductionThe literature on vanadium alkoxide chemistry describes a number of high valence, vanadium(V) compounds prepared from commercially available VOCl 3 , V 2 O 5 , (NH 4 )VO 3 or VO(OR) 3 (R = alkyl). These species have received attention because of their applications as catalysts in polymerization reactions 1 and as precursors of industrially applied homo-and mixed-metal oxides.2 There is also an increasing interest on the preparation of lower oxidation state vanadium alkoxides, such as non-oxo vanadium(III)/ (IV) compounds, to be employed as direct precursors of less common oxides without the use of reducing reaction conditions.3 However, these syntheses have been hampered by the lack of suitable non-oxo starting materials, as the very stable v...

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