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Volumn 60, Issue 3, 2013, Pages 455-470

Strong cationic oxidizers: Thermal decomposition, electronic structure and magnetism of their compounds

Author keywords

Electronic structure; Fluorides; Magnetism; Oxides; Oxidizer; Silver

Indexed keywords

ANION; CATION;

EID: 84883644633     PISSN: 13180207     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Review
Times cited : (16)

References (121)
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    • 0value exceeds +3.0 V vs. NHE
    • 0value exceeds +3.0 V vs. NHE.
  • 3
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    • 0values for the highest oxidation states of Pu (VII, VI) in acidic environment are not available; also, it is not unreasonable that Pu(VIII)O4 could exist
    • 0values for the highest oxidation states of Pu (VII, VI) in acidic environment are not available; also, it is not unreasonable that Pu(VIII)O4 could exist.
  • 4
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    • In disagreement with the values listed here, some experiments suggest that at certain conditions NiF3 + is a stronger oxidizer than PtF6 but whether its oxidizing strength exceeds that of KrF+ remains unclear: T. Schroer, K. O. Christe, Inorg. Chem. 2001, 40, 2415-2419.
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    • Western Oregon University data, accessed on Apr 12, 2012
    • Western Oregon University data; http://www.wou.edu/las/physci/ch412/ redox.htm accessed on Apr 12, 2012.
  • 17
    • 84881100083 scopus 로고    scopus 로고
    • in press, doi: 10.1039/c3cc43072c
    • The value of +1.98 V is frequently given in textbooks. Our recent study shows that the formal redox potential, E0', may reach up to +2.9 V vs. NHE for Ag(II) dissolved in 33% oleum: P. Połczyński, R. Jurczakowski, W. Grochala, Chem. Commun., in press 2013, doi: 10.1039/c3cc43072c.
    • (2013) Chem. Commun.
    • Połczyński, P.1    Jurczakowski, R.2    Grochala, W.3
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    • 2nd Ed., G. Brauer, Academic Press New York
    • Preparative chemistry textbooks contain warning that PbCl4 could spontaneously explode and preparation of larger amounts of this compound is not advisable. It should be stored at temperatures below -80 °C and protected from sunlight. See for example: Handbook of Preparative Inorganic Chemistry, Vol. 1, 2nd Ed., G. Brauer, Academic Press New York 1963, p.751.
    • (1963) Handbook of Preparative Inorganic Chemistry , vol.1 , pp. 751
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    • The data for pure related CoO2 are missing, specimen containing water have been studied: C. B. Wang, H. K. Lin, C. W. Tang, Cat. Lett., 2004, 94, 69-74.
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    • Wang, C.B.1    Lin, H.K.2    Tang, C.W.3
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    • These authors feel that possibility of its facile collapse to U(VI)(O22-) has not been sufficiently addressed
    • Unusual U(XII)O6 has been postulated: P. Pyykkö, N. Runeberg, M. Straka, K. G. Dyall, Chem. Phys. Lett., 2000, 328, 415-419. These authors feel that possibility of its facile collapse to U(VI)(O22-) has not been sufficiently addressed.
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    • Elsevier, Amsterdam, chapter 6.11.2 and references therein
    • See: L. Piela, Ideas of quantum chemistry, Elsevier, Amsterdam 2007, chapter 6.11.2 and references therein.
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    • Physics & Chemistry at low temperatures, ed. by L. Khriachtchev, Pan Stanford Publishing
    • For a recent review of oxidizers containing noble gas atoms see: W. Grochala, L. Khriachtchev, M. Räsänen, Noble Gas Chemistry, in: Physics & Chemistry at low temperatures, ed. by L. Khriachtchev, Pan Stanford Publishing 2011, 421-448.
    • (2011) Noble Gas Chemistry , pp. 421-448
    • Grochala, W.1    Khriachtchev, L.2    Räsänen, M.3
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    • To our disappointment, we have not found any previous case of the inversion of metal-ligand states which would be well documented via quantum mechanical calculations and quantitative analysis of atomic contributions to the density o states, F4 (see Ref. 65) thus seems to be the first of the kind
    • To our disappointment, we have not found any previous case of the inversion of metal-ligand states which would be well documented via quantum mechanical calculations and quantitative analysis of atomic contributions to the density o states. The case of KAg(III)F4 (see Ref. 65) thus seems to be the first of the kind.
    • The Case of KAg(III)
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    • The crossing of electronic states was postulated to be the reason for so called "bond stretch isomerism" but the original explanation did not involve the genuine redox process. See or example: Y. Jean, A. Lledos, J. K. Burdett, R. Hoffmann, J. Am. Chem. Soc. 1988, 110, 4506-4516
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    • G. Parkin, R. Hoffmann, Angew. Chem. Int. Ed. Engl., 1994, 33, 1462-1462, and references therein. The experimental findings which inspired the discussion on bond stretch isomerism later proved incorrect, nevertheless the theoretical arguments are valid and a real case of bond stretch isomerism might be found in the future.
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    • One example of how one may systematically play the metalligand redox equilibrium and use it as a base for molecular memory is given in: A. Sokołowski, W. Grochala, J. Mol. Model. 2005, 11, 278-287.
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    • For atomic DOS analysis of higher silver oxides, AgO i.e. Ag(I))Ag(III)O2, and Ag(III)2O3 cf.: J. P. Allen, D. O. Scanlon, G. W. Watson, Phys. Rev. B 2011, 84, 115141-1 to -14.
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    • Allen, J.P.1    Scanlon, D.O.2    Watson, G.W.3
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    • This simple tool was first introduced in the comparative study of CaCuO2 and hypothetical flat-layer AgF2 and it served to emphasize similarities between both compounds: W. Grochala, Scripta Mater., 2006, 55, 811-814.
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    • As a referee correctly reminded us, PtF6 has a null number of unpaired electrons. This comes from spin-orbit splitting of the t2g levels as first pointed out by Moffit et al. This agrees with the absorption spectra in the near infrared, the IR and Raman spectra showing undisturbed octahedral symmetry (i.e. no Jahn-Teller effect in contrast to IrF6, OsF6, and Re-F6), the possibility to obtain highly resolved 19F and 195Pt NMR spectra, and with the temperature independent small paramagnetism: W. Moffitt, G. L. Goodman, M. Fred, B. Weinstock, Mol. Phys. 1959, 2, 109-122.
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    • Magnetic susceptibility of the elements and inorganic compounds
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    • Magnetic behaviour for some has not been measured and even molar susceptibilities at room temperature have not been determined; cf. Magnetic susceptibility of the elements and inorganic compounds, in: CRC «Handbook of Chemistry and Physics» D.R. Lide, Ed., New York, 81st ed., CRC Press, 2001.
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    • The extrapolation from the Curie-Weiss law has been performed for rather small temperatures, and the real value of ∪ must be larger than that. The theoretical estimate from DFT calculations is ca. -40 meV: D. Kurzydłowski, private communication to the author
    • The extrapolation from the Curie-Weiss law has been performed for rather small temperatures, and the real value of ∪ must be larger than that. The theoretical estimate from DFT calculations is ca. -40 meV: D. Kurzydłowski, private communication to the author.


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