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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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. |
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ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/c5dt00339c |