Rates of ligand exchange between > Fe-III-OH2 functional groups on a nanometer-sized aqueous cluster and bulk solution

Balogh E, Todea AM, Müller A, Casey WH (2007)
INORGANIC CHEMISTRY 46(17): 7087-7092.

Journal Article | Published | English

No fulltext has been uploaded

Author
; ; ;
Abstract
Variable-temperature O-17 NMR experiments were conducted on the nanometer-sized Keplerate MO72Fe30 cluster, with the stoichiometry [MO72Fe30O252(CH3COO)(12)[MO2O7(H2O)](2)[H2MO2O8(H2O)(91)]center dot similar to(H2O)91]center dot similar to 150H(2)O. This molecule contains on its surface 30 Fe(H2O) groups forming a well-defined icosidodecahedron, and we estimated the rates of exchange of the isolated >Fe-III-OH2 waters with bulk aqueous solution, Both longitudinal and transverse O-17-relaxation times were measured, as well as chemical shifts, and these parameters were then fit to the Swift-Connick equations in order to obtain the rate parameters. Correspondingly, we estimate: k(ex)(298) = 6.7(+/- 0.8) x 10(6) s(-1), which is about a factor of similar to 4 x 10(4) times larger than the corresponding rate coefficient for the Fe(OH2)(6)(3+) ion of k(ex)(298) = 1.6 x 10(2) S-1 (Grant and Jordan, 1981; Inorg. Chem. 20, 55-60) and Delta H double dagger and Delta S double dagger are 26.3 +/- 0.6 kj mol(-1) and -26 +/- 0.9 J mol(-1) K-1, respectively. High-pressure 110 NMR experiments were also conducted, but the cluster decomposed slightly under pressure, which precluded confident quantitative estimation of the AV. However, the increase in the reduced transverse-relaxation time with pressure suggests a dissociative character, such as a D or Id mechanism. The enhanced reactivity of waters on the MO72Fe30 cluster is associated with an increase in the Fe-III-OH2 bond length in the solid state of similar to 0.1 angstrom relative to the Fe(OH2)(6)(3+) ion, suggesting that a correlation exists between the Fe-III-OH2 bond length and k(ex)(298). Although there are only few high-spin Fe(III) complexes where both exchange rates and structural data are available, these few seem to support a general correlation.
Publishing Year
ISSN
eISSN
PUB-ID

Cite this

Balogh E, Todea AM, Müller A, Casey WH. Rates of ligand exchange between > Fe-III-OH2 functional groups on a nanometer-sized aqueous cluster and bulk solution. INORGANIC CHEMISTRY. 2007;46(17):7087-7092.
Balogh, E., Todea, A. M., Müller, A., & Casey, W. H. (2007). Rates of ligand exchange between > Fe-III-OH2 functional groups on a nanometer-sized aqueous cluster and bulk solution. INORGANIC CHEMISTRY, 46(17), 7087-7092.
Balogh, E., Todea, A. M., Müller, A., and Casey, W. H. (2007). Rates of ligand exchange between > Fe-III-OH2 functional groups on a nanometer-sized aqueous cluster and bulk solution. INORGANIC CHEMISTRY 46, 7087-7092.
Balogh, E., et al., 2007. Rates of ligand exchange between > Fe-III-OH2 functional groups on a nanometer-sized aqueous cluster and bulk solution. INORGANIC CHEMISTRY, 46(17), p 7087-7092.
E. Balogh, et al., “Rates of ligand exchange between > Fe-III-OH2 functional groups on a nanometer-sized aqueous cluster and bulk solution”, INORGANIC CHEMISTRY, vol. 46, 2007, pp. 7087-7092.
Balogh, E., Todea, A.M., Müller, A., Casey, W.H.: Rates of ligand exchange between > Fe-III-OH2 functional groups on a nanometer-sized aqueous cluster and bulk solution. INORGANIC CHEMISTRY. 46, 7087-7092 (2007).
Balogh, Edina, Todea, Ana Maria, Müller, Achim, and Casey, William H. “Rates of ligand exchange between > Fe-III-OH2 functional groups on a nanometer-sized aqueous cluster and bulk solution”. INORGANIC CHEMISTRY 46.17 (2007): 7087-7092.
This data publication is cited in the following publications:
This publication cites the following data publications:

11 Citations in Europe PMC

Data provided by Europe PubMed Central.

Keplerate cluster (Mo-132) mediated electrostatic assembly of nanoparticles.
Gooch J, Jalan AA, Jones S, Hine CR, Alam R, Garai S, Maye MM, Muller A, Zubieta J., J Colloid Interface Sci 432(), 2014
PMID: 25086388
Electronic structure and soft-X-ray-induced photoreduction studies of iron-based magnetic polyoxometalates of type {(M)M5}12Fe(III)30 (M = Mo(VI), W(VI)).
Kuepper K, Derks C, Taubitz C, Prinz M, Joly L, Kappler JP, Postnikov A, Yang W, Kuznetsova TV, Wiedwald U, Ziemann P, Neumann M., Dalton Trans 42(22), 2013
PMID: 23403844
Self-recognition among different polyprotic macroions during assembly processes in dilute solution.
Liu T, Langston ML, Li D, Pigga JM, Pichon C, Todea AM, Muller A., Science 331(6024), 2011
PMID: 21436449
Porous capsules {(M)M(5)}(12)Fe(III) (30) (M=Mo(VI), W(VI)): sphere surface supramolecular chemistry with 20 ammonium ions, related solution properties, and tuning of magnetic exchange interactions.
Todea AM, Merca A, Bogge H, Glaser T, Pigga JM, Langston ML, Liu T, Prozorov R, Luban M, Schroder C, Casey WH, Muller A., Angew. Chem. Int. Ed. Engl. 49(3), 2010
PMID: 20013836
Dissolution of insulating oxide materials at the molecular scale.
Ohlin CA, Villa EM, Rustad JR, Casey WH., Nat Mater 9(1), 2010
PMID: 20019664
Gated and differently functionalized (new) porous capsules direct encapsulates' structures: higher and lower density water.
Mitra T, Miro P, Tomsa AR, Merca A, Bogge H, Avalos JB, Poblet JM, Bo C, Muller A., Chemistry 15(8), 2009
PMID: 19130528
Functionalization of polyoxometalates: towards advanced applications in catalysis and materials science.
Proust A, Thouvenot R, Gouzerh P., Chem. Commun. (Camb.) (16), 2008
PMID: 18401495

Export

0 Marked Publications

Open Data PUB

Web of Science

View record in Web of Science®

Sources

PMID: 17661461
PubMed | Europe PMC

Search this title in

Google Scholar