| 1. |
- Ohlin, C. Andre, et al.
(author)
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Rates of Water Exchange for Two Cobalt(II) Heteropolyoxotungstate Compounds in Aqueous Solution
- 2011
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In: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 17:16, s. 4408-4417
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Journal article (peer-reviewed)abstract
- Polyoxometalate ions are used as ligands in water-oxidation processes related to solar energy production. An important step in these reactions is the association and dissociation of water from the catalytic sites, the rates of which are unknown. Here we report the exchange rates of water ligated to Co-II atoms in two polyoxotungstate sandwich molecules using the O-17-NMR-based Swift-Connick method. The compounds were the [Co-4(H2O)(2)(B-alpha-PW9O34)(2)](10-) and the larger alpha beta beta alpha-[Co-4(H2O)(2)(P2W15O56)(2)](16-) ions, each with two water molecules bound trans to one another in a Co-II sandwich between the tungstate ligands. The clusters, in both solid and solution state, were characterized by a range of methods, including NMR, EPR, FT-IR, UV-Vis, and EXAFS spectroscopy, ESI-MS, single-crystal Xray crystallography, and potentiometry. For [Co-4(H2O)(2)(B-alpha-PW9O34)(2)](10-) at pH 5.4, we estimate: k(298) = 1.5(5) +/- 0.3 x 10(6) s(-1), Delta H-not equal = 39.8 +/- 0.4 kJ mol(-1), Delta S-not equal = + 7.1 +/- 1.2 J mol(-1)K(-1) and Delta V-not equal = 5.6 +/- 1.6 cm(3)mol(-1). For the Wells-Dawson sandwich cluster (alpha beta beta alpha-[Co-4(H2O)(2)(P2W15O56)(2)](16-)) at pH 5.54, we find: k(298) = 1.6(2) +/- 0.3 x 10(6)s(-1), Delta H-not equal = 27.6 +/- 0.4 kJ mol(-1) Delta S-not equal = -33 +/- 1.3 J mol(-1)K(-1) and Delta V-not equal = 2.2 +/- 1.4 cm(3)mol(-1) at pH 5.2. The molecules are clearly stable and monospecific in slightly acidic solutions, but dissociate in strongly acidic solutions. This dissociation is detectable by EPR spectroscopy as S=3/2 Co-II species (such as the [Co(H2O)(6)](2+) monomer ion) and by the significant reduction of the Co-Co vector in the XAS spectra.
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| 2. |
- Stich, Troy A., et al.
(author)
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Structural insights into [Co4O4(C5H5N)(4)(CH3CO2)(4)](+), a rare Co(IV)-containing cuboidal complex
- 2013
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In: Polyhedron. - : Elsevier BV. - 0277-5387 .- 1873-3719. ; 64:SI, s. 304-307
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Journal article (peer-reviewed)abstract
- We report high-frequency (up to 219 GHz) and correspondingly high-field electron paramagnetic resonance spectra and X-ray crystal structure of [Co4O4(pyridine)(4)(acetate)(4)](+) ([Co4O4(py)(4)(OAc)(4)](+)) that serves as a structural and spectroscopic model of cobalt-oxide films that are capable of oxidizing water. These results are, in large part, consistent with those from our earlier, lower-frequency study and serve to benchmark future high-field studies on paramagnetic states of the catalyst film. (C) 2013 Published by Elsevier Ltd.
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