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Hennig C, Ikeda-Ohno A, Kraus W, et al. Crystal structure and solution species of Ce(III) and Ce(IV) formates: from mononuclear to hexanuclear complexes. Inorg Chem. 2013;52(20):11734-43doi: 10.1021/ic400999j.
Hennig, C., Ikeda-Ohno, A., Kraus, W., Weiss, S., Pattison, P., Emerich, H., Abdala, P. M., & Scheinost, A. C. (2013). Crystal structure and solution species of Ce(III) and Ce(IV) formates: from mononuclear to hexanuclear complexes. Inorganic chemistry, 52(20), 11734-43. https://doi.org/10.1021/ic400999j
Hennig, Christoph, et al. "Crystal structure and solution species of Ce(III) and Ce(IV) formates: from mononuclear to hexanuclear complexes." Inorganic chemistry vol. 52,20 (2013): 11734-43. doi: https://doi.org/10.1021/ic400999j
Hennig C, Ikeda-Ohno A, Kraus W, Weiss S, Pattison P, Emerich H, Abdala PM, Scheinost AC. Crystal structure and solution species of Ce(III) and Ce(IV) formates: from mononuclear to hexanuclear complexes. Inorg Chem. 2013 Oct 21;52(20):11734-43. doi: 10.1021/ic400999j. Epub 2013 Oct 03. PMID: 24090406.
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Inorg Chem. 2013 Oct 21;52(20):11734-43. doi: 10.1021/ic400999j. Epub 2013 Oct 03.

Crystal structure and solution species of Ce(III) and Ce(IV) formates: from mononuclear to hexanuclear complexes.

Inorganic chemistry

Christoph Hennig, Atsushi Ikeda-Ohno, Werner Kraus, Stephan Weiss, Philip Pattison, Hermann Emerich, Paula M Abdala, Andreas C Scheinost

Affiliations

  1. Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology , Bautzner Landstrasse 400, D-01314 Dresden, Germany.

PMID: 24090406 DOI: 10.1021/ic400999j

Abstract

Cerium(III) and cerium(IV) both form formate complexes. However, their species in aqueous solution and the solid-state structures are surprisingly different. The species in aqueous solutions were investigated with Ce K-edge EXAFS spectroscopy. Ce(III) formate shows only mononuclear complexes, which is in agreement with the predicted mononuclear species of Ce(HCOO)(2+) and Ce(HCOO)2(+). In contrast, Ce(IV) formate forms in aqueous solution a stable hexanuclear complex of [Ce6(μ3-O)4(μ3-OH)4(HCOO)x(NO3)y](12-x-y). The structural differences reflect the different influence of hydrolysis, which is weak for Ce(III) and strong for Ce(IV). Hydrolysis of Ce(IV) ions causes initial polymerization while complexation through HCOO(-) results in 12 chelate rings stabilizing the hexanuclear Ce(IV) complex. Crystals were grown from the above-mentioned solutions. Two crystal structures of Ce(IV) formate were determined. Both form a hexanuclear complex with a [Ce6(μ3-O)4(μ3-OH)4](12+) core in aqueous HNO3/HCOOH solution. The pH titration with NaOH resulted in a structure with the composition [Ce6(μ3-O)4(μ3-OH)4(HCOO)10(NO3)2(H2O)3]·(H2O)9.5, while the pH adjustment with NH3 resulted in [Ce6(μ3-O)4(μ3-OH)4(HCOO)10(NO3)4]·(NO3)3(NH4)5(H2O)5. Furthermore, the crystal structure of Ce(III) formate, Ce(HCOO)3, was determined. The coordination polyhedron is a tricapped trigonal prism which is formed exclusively by nine HCOO(-) ligands. The hexanuclear Ce(IV) formate species from aqueous solution is widely preserved in the crystal structure, whereas the mononuclear solution species of Ce(III) formate undergoes a polymerization during the crystallization process.

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