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Nelson AG, Bray TH, Zhan W, et al. Further examples of the failure of surrogates to properly model the structural and hydrothermal chemistry of transuranium elements: insights provided by uranium and neptunium diphosphonates. Inorg Chem. 2008;47(11):4945-51doi: 10.1021/ic800255h.
Nelson, A. G., Bray, T. H., Zhan, W., Haire, R. G., Sayler, T. S., & Albrecht-Schmitt, T. E. (2008). Further examples of the failure of surrogates to properly model the structural and hydrothermal chemistry of transuranium elements: insights provided by uranium and neptunium diphosphonates. Inorganic chemistry, 47(11), 4945-51. https://doi.org/10.1021/ic800255h
Nelson, Anna-Gay D, et al. "Further examples of the failure of surrogates to properly model the structural and hydrothermal chemistry of transuranium elements: insights provided by uranium and neptunium diphosphonates." Inorganic chemistry vol. 47,11 (2008): 4945-51. doi: https://doi.org/10.1021/ic800255h
Nelson AG, Bray TH, Zhan W, Haire RG, Sayler TS, Albrecht-Schmitt TE. Further examples of the failure of surrogates to properly model the structural and hydrothermal chemistry of transuranium elements: insights provided by uranium and neptunium diphosphonates. Inorg Chem. 2008 Jun 02;47(11):4945-51. doi: 10.1021/ic800255h. Epub 2008 May 02. PMID: 18452285.
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Inorg Chem. 2008 Jun 02;47(11):4945-51. doi: 10.1021/ic800255h. Epub 2008 May 02.

Further examples of the failure of surrogates to properly model the structural and hydrothermal chemistry of transuranium elements: insights provided by uranium and neptunium diphosphonates.

Inorganic chemistry

Anna-Gay D Nelson, Travis H Bray, Wei Zhan, Richard G Haire, Todd S Sayler, Thomas E Albrecht-Schmitt

Affiliations

  1. Department of Chemistry and Biochemistry and Center for Actinide Science, Auburn University, Auburn, Alabama 36849, USA.

PMID: 18452285 DOI: 10.1021/ic800255h

Abstract

In situ hydrothermal reduction of Np(VI) to Np(IV) in the presence of methylenediphosphonic acid (C1P2) results in the crystallization of Np[CH2(PO3)2](H2O)2 (NpC1P2-1). Similar reactions have been explored with U(VI) resulting in the isolation of the U(IV) diphosphonate U[CH2(PO3)2](H2O) (UC1P2-1), and the two U(VI) diphosphonates (UO2)2[CH2(PO3)2](H2O)3.H2O (UC1P2-2) and UO2[CH2(PO3H)2](H2O) (UC1P2-3). Single crystal diffraction studies of NpC1P2-1 reveal that it consists of eight-coordinate Np(IV) bound by diphosphonate anions and two coordinating water molecules to create a polar three-dimensional framework structure wherein the water molecules reside in channels. The structure of UC1P2-1 is similar to that of NpC1P2-1 in that it also adopts a three-dimensional structure. However, the U(IV) centers are seven-coordinate with only a single bound water molecule. UC1P2-2 and UC1P2-3 both contain U(VI). Nevertheless, their structures are quite distinct with UC1P2-2 being composed of corrugated layers containing UO 6 and UO 7 units bridged by C1P2; whereas, UC1P2-3 is found as a polar three-dimensional network structure containing only pentagonal bipyramidal U(VI). Fluorescence measurements on UC1P2-2 and UC1P2-3 exhibit emission from the uranyl moieties with classical vibronic fine-structure.

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