Chemistry of hydrotrioxides. A comparative ab initio study of the equilibrium structures of monomeric and dimeric hydrotrioxides (CH sub 3 OOOH, H sub 3 SiOOOH) and hydroperoxides (CH sub 3 OOH, H sub 3 SiOOH). Relative bond strengths in and the gas-phase acidities of hydrotrioxides and hydroperoxides

Journal Article · Wed Mar 14 04:00:00 EST 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00162a013· OSTI ID:6383011

Koller, J; Hodoscek, M; Plesnicar, B ^[1]

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1. Edvard Kardelj Univ., Ljubljana (Yugoslavia)

Ab initio calculations have been carried out to predict the equilibrium structures of monomeric and dimeric CH{sub 3}OOOH, H{sub 3}SiOOOH, CH{sub 3}OOH, and H{sub 3}SiOOH. The calculated relatively strong binding energies for the intermolecularly hydrogen-bonded cyclic dimers of the hydrotrioxides and hydroperoxides investigated (BE = 6-8 kcal/mol) support the belief that self-association is the characteristic structural feature of these species. Ab initio calculations of the theoretical acidities, defined as the energy differences between the energy minima for the neutral molecules and those for the corresponding anions, reveal the following order of the gas-phase acidities: H{sub 3}SiOOOH > CH{sub 3}OOOH > H{sub 3}SiOOH > CH{sub 3}OOH. The investigation of relative bond strengths indicates that the RO-OOH bonds in the hydrotrioxides are weaker than the ROO-OH bonds, supporting the predictions from the previous thermochemical and kinetic studies that the split into RO{sm bullet} and {sm bullet}OOH radicals is the lowest energy radical decomposition pathway available for these polyoxides.

• OSTI ID: 6383011
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:6; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BINDING ENERGY
CALCULATION METHODS
CHALCOGENIDES
DIMERS
ENERGY
MATHEMATICAL MODELS
MOLECULAR ORBITAL METHOD
MOLECULAR STRUCTURE
OXIDES
OXYGEN COMPOUNDS