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Published on: February 14, 2014
Where are the protons in alpha-[H(x)W(12)O(40)](8-x)- (x = 2-4)?
Calvin R Sprangers1, Jason K Marmon, Dean C Duncan
1Department of Chemistry and Biochemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, USA.
The polyoxometalate alpha-(H2)W(12)O(40)]6- (1) reversibly binds one proton in its internal cavity in non-aqueous media. This protonation is rapid, but the reverse reaction is slow, indicating a significant activation barrier.
Area of Science:
- Inorganic Chemistry
- Supramolecular Chemistry
- Materials Science
Background:
- Polyoxometalates (POMs) are versatile inorganic clusters with tunable properties.
- The cryptate polyoxometalate alpha-(H2)W(12)O(40)]6- (1) features an internal cavity capable of hosting guest species.
- Protonation states and locations within POMs are often debated, necessitating detailed structural and dynamic studies.
Purpose of the Study:
- To elucidate the protonation equilibria and speciation of the cryptate polyoxometalate 1 in non-aqueous media.
- To clarify the number and location of protons accommodated by the internal cavity of 1.
- To investigate the kinetics of protonation and deprotonation of 1.
Main Methods:
- Phase-transfer cation metathesis to synthesize tetrabutylammonium (Q+) salts of 1.
- Nuclear Magnetic Resonance (NMR) spectroscopy (1H and 183W) for structural and dynamic analysis.
- Elemental analysis, acid titration, and H/D isotopomer studies to confirm protonation states.
Main Results:
- Isolation and characterization of Q(6)1 and alpha-Q5[(H3)W(12)O(40)](Q(5)2).
- Spectroscopic and analytical evidence confirms that 1 reversibly accommodates only one additional proton in its internal cavity in non-aqueous media, forming species 2.
- Protonation of 1 is instantaneous, while deprotonation is slow (t1/2 ≈ 17.4 h), suggesting a substantial activation barrier for proton transfer across the tungsten oxide surface.
Conclusions:
- The internal cryptand cavity of polyoxometalate 1 can accommodate a maximum of one additional proton in non-aqueous solvents.
- The observed kinetic asymmetry in protonation/deprotonation highlights the influence of the POM surface on proton transfer dynamics.
- This study provides definitive insights into the protonation behavior of cryptate polyoxometalates, resolving previous ambiguities.
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