Understanding the Scarcity of Thorium Peroxide Clusters

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.