Understanding the Scarcity of Thorium Peroxide Clusters

Autor: Shane S. Galley, Thomas E. Albrecht-Schmitt, Cayla E. Van Alstine, Laurent Maron
Přispěvatelé: Department of Chemistry and Biochemistry, Tallahassee (DCB), Florida State University [Tallahassee] (FSU), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Rok vydání: 2017
Předmět:
Zdroj: Inorganic Chemistry
Inorganic Chemistry, American Chemical Society, 2017, 56 (21), pp.12692-12694. ⟨10.1021/acs.inorgchem.7b02216⟩
Inorganic Chemistry, American Chemical Society, 2017, 56 (21), pp.12692--12694
Inorganic Chemistry, 2017, 56 (21), pp.12692-12694. ⟨10.1021/acs.inorgchem.7b02216⟩
ISSN: 1520-510X
0020-1669
DOI: 10.1021/acs.inorgchem.7b02216
Popis: bibtex: ISI:000414820100007 bibtex\location:'1155 16TH ST, NW, WASHINGTON, DC 20036 USA',publisher:'AMER CHEMICAL SOC',type:'Article',affiliation:'Albrecht-Schmitt, TE (Reprint Author), Florida State Univ, Dept Chem & Biochem, Tallahassee, FL 32306 USA. Galley, Shane S.; Van Alstine, Cayla E.; Albrecht-Schmitt, Thomas E., Florida State Univ, Dept Chem & Biochem, Tallahassee, FL 32306 USA. Maron, Laurent, Inst Natl Sci Appl, Lab Phys & Chim Nanoobjets, F-31077 Toulouse 4, France.','author-email':'albrecht-schmitt@chem.fsu.edu',da:'2018-12-05','doc-delivery-number':'FM2MY',eissn:'1520-510X','funding-acknowledgement':'Center for Actinide Science and Technology, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0016568]','funding-text':'This work was supported as part of the Center for Actinide Science and Technology, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award DE-SC0016568.','journal-iso':'Inorg. Chem.','keywords-plus':'MOLECULAR-ORBITAL METHODS; VALENCE BASIS-SETS; ENERGY; PSEUDOPOTENTIALS; ACTINIDES; EXCHANGE; ELEMENTS; IR','number-of-cited-references':'26','orcid-numbers':'Albrecht-Schmitt, Thomas/0000-0002-2989-3311','research-areas':'Chemistry','times-cited':'2','unique-id':'ISI:000414820100007','usage-count-last-180-days':'2','usage-count-since-2013':'14','web-of-science-categories':'Chemistry, Inorganic & Nuclear'\; International audience; The reaction of Th(NO3)(4)center dot 5H(2)O with 3 equiv of 2,2',6',2\''\-terpyridine (terpy) in a mixture of acetonitrile and methanol results in formation of the trinuclear thorium peroxide cluster \[\Th(O-2)(terpy)-(NO3)(2)](3). This cluster is assembled via bridging by mu eta(2):eta(2) peroxide anions between thorium centers. It decomposes upon removal from the mother liquor to yield Th(terpy)(NO3)(4) and Th(terpy)(NO3)(4)(EtOH). The peroxide formation appears to be radiolytic in origin and is, most likely, generated from radiolysis of water by short-lived daughters generated from Th-232 decay. This cluster does not form when freshly recrystallized Th(NO3)(4)center dot 5H(2)O is used as the starting material and requires an aged source of thorium. Analysis of the bonding in these clusters shows that, unlike uranium(VI) peroxide interactions, thorium(IV) complexation by peroxide is quite weak and largely ionic. This explains its much lower stability, which is more comparable to that observed in similar zirconium(IV) peroxide clusters.
Databáze: OpenAIRE
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