A convenient and quantitative route to Sn(iv)-M [M = Ti(iv), Nb(v), Ta(v)] heterobimetallic precursors for dense mixed-metal oxide ceramicsElectronic supplementary information (ESI) available: FT-IR, 1H and 119Sn NMR spectra of the new complexes, molecular structures with selected bond lengths (Å) and angles (°) of 1a, 1b, 4a, 6 and 8, DFT-optimized structures of 4-6 and related model compounds, dilatograms related to the Spark Plasma Sintering of the pre-calcined Sn0.5Ti0.5O2 powders, and 9 X-r

The strategy of reacting SnCl 4 with M(OR) x provided a convenient and quantitative approach to new heterobimetallics with a simple addition formula, [SnCl 4 M(OR) x (HOR) y ] (M = Ti, Nb, Ta; R = Et, Pr i , x = 4, 5; y = 0-2) or sometimes an oxo complex [SnCl 3 (O)Ti 2 (OPr i ) 7 (HOPr i ) 2 ]. The...

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Hauptverfasser: Mishra, Shashank, Jeanneau, Erwann, Mangematin, Stéphane, Chermette, Henry, Poor Kalhor, Mahboubeh, Bonnefont, Guillaume, Fantozzi, Gilbert, Le Floch, Sylvie, Pailhes, Stéphane, Daniele, Stéphane
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Sprache:eng
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Zusammenfassung:The strategy of reacting SnCl 4 with M(OR) x provided a convenient and quantitative approach to new heterobimetallics with a simple addition formula, [SnCl 4 M(OR) x (HOR) y ] (M = Ti, Nb, Ta; R = Et, Pr i , x = 4, 5; y = 0-2) or sometimes an oxo complex [SnCl 3 (O)Ti 2 (OPr i ) 7 (HOPr i ) 2 ]. The alcoholysis reactions of these heterometallics afforded mixed alkoxo complexes [SnCl 4 (μ-OEt) 2 M(Pr i O) x (Pr i OH) y ] [M = Ti ( x = y = 2), Nb, Ta ( x = 3, y = 1)] under mild conditions, or a planar rectangular oxo product [SnCl 3 (μ-OEt) 2 Nb(OEt) 2 (EtOH)(μ-O)] 2 at refluxing/extended stirring time. DFT calculations shed light on the stability and reactivity of these complexes. The use of these thoroughly characterized heterometallics as sol-gel precursors suppresses the formation of the undesired SnO 2 grains, which are difficult to be sintered to a high density. The combined approach of using bottom-up synthesis of mixed Ti 0.5 Sn 0.5 O 2 nanoparticles and Spark Plasma Sintering allowed the successful densification of chloride-free mixed-metal oxide ceramics. The influence of thermal treatment before sintering on the density and spinodal decomposition of the TiO 2 -SnO 2 pellets is reported. Simplicity is beauty. Reactions of SnCl 4 with M(OR) x yield novel heterobimetallics with simple addition formula.
ISSN:1477-9226
1477-9234
DOI:10.1039/c5dt00339c