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Penta- and tetracarbonyls of Ru, Os, and Hs: electronic structure, bonding, and volatility

  1. TitlePenta- and tetracarbonyls of Ru, Os, and Hs: electronic structure, bonding, and volatility
    Author infoV. Pershina, M. Iliaš
    Author Pershina Valeria (50%)
    Co-authors Iliaš Miroslav 1975- (50%) UMBFP08 - Katedra chémie
    Source document The Journal of Chemical Physics. Vol. 146, no. 18 (2017), art. no. 184306. - New York : American Institute of Physics, 2017
    Keywords karbonylové zlúčeniny   tetrakarbonyly - tetracarbonyls   pentakarbonyly - pentacarbonyls  
    LanguageEnglish
    CountryUnited States of America
    systematics 544
    AnnotationCalculations of the electronic structures and properties of M(CO)(5) and M(CO)(4), where M = Ru, Os, and Hs, have been performed using a variety of relativistic methods such as density functional theory and Dirac-Coulomb correlated ones implemented in program packages such as ADF, DIRAC, and ReSpect. The obtained results show that trends in spectroscopic properties of the M(CO)(5) species in group 8 follow the same pattern as that of other compounds of group 4 through group 8 elements. The calculated first M-CO bond dissociation energy (FBDE) of Hs(CO)(5) turned out to be significantly weaker than that of Os(CO)(5). This was obtained both at the scalar relativistic and spin-orbit levels of theory. The reason for that is the relativistic destabilization and the expansion of the 6d AOs, responsible for weaker sigma-forth and pi-back donations in the Hs compound. Thus, the FBDEs of M(CO)(5) have a Lambda-shape behavior in the row Ru-Os-Hs. The non-relativistic FBDEs steadily increase in this row. Using the results of the molecular calculations and a molecule-slab dispersion interaction model, the volatility of the group-8 carbonyls was estimated as adsorption enthalpies, Delta H-ads, on surfaces of quartz and Teflon used in gas-phase chromatography experiments. It was found that Hs(CO)(5) should be almost as volatile as the homologs; however, its interaction strength with these surfaces should be somewhat larger than that of both Ru(CO)(5) and Os(CO)(5), while the M(CO)(4) (M = Ru, Os, and Hs) molecules should be non-volatile. It will, therefore, be difficult to distinguish between group-8 M(CO)(5) species by measurements of their volatility as Delta H-ads on inert surfaces with error bars of similar to 4 kJ/mol. Published by AIP Publishing.
    Public work category ADC
    No. of Archival Copy39962
    Catal.org.BB301 - Univerzitná knižnica Univerzity Mateja Bela v Banskej Bystrici
    Databasexpca - PUBLIKAČNÁ ČINNOSŤ
    ReferencesPERIODIKÁ-Súborný záznam periodika
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