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Inorg Chem. 2011 Sep 5;50(17):8621-9. doi: 10.1021/ic201175u. Epub 2011 Aug 3.

Synthesis and characterization of thorium(IV) sulfates.

Author information

1
Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA.

Abstract

Three Th(IV) sulfates, two new and one previously reported, have been synthesized from aqueous solution. In all of the compounds, the sulfate anions coordinate the Th(4+) metal center(s) in a monodentate manner with Th-S distances of 3.7-3.8 Å. Th(SO(4))(2)(H(2)O)(7)·2(H(2)O) (1; P2(1)/m, a = 7.224(1) Å, b = 12.151(1) Å, c = 7.989(1) Å, ss =98.289(2)°) and Th(4)(SO(4))(7)(H(2)O)(7)(OH)(2)·H(2)O (2; Pnma, a = 18.139(2) Å, b = 11.173(1) Å, c = 14.391(2) Å) each contain 9-coordinate monomeric (1,2) and dimeric (2) Th(IV) cations in monocapped square antiprism geometry. Alternatively, Th(OH)(2)SO(4) (3; Pnma, a = 11.684(1) Å, b = 6.047(1) Å, c = 7.047(1) Å) is built from chains of hydroxo-bridged, 8-coordinate Th(4+) centers. Whereas 1 adopts a molecular structure, 2 and 3 both exhibit 3D architectures. Differences in the dimensionality and the topology of 1-3 are manifested in the local coordination environment about the Th(IV) centers, the formation of oligomeric Th(4+) species, and the extended connectivity of the sulfate ligands. Herein, we report the syntheses and characterization of 1-3 as well as the atomic correlations of 1 in solution, as determined by high-energy X-ray scattering (HEXS).

PMID:
21812466
DOI:
10.1021/ic201175u
[Indexed for MEDLINE]

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