Gas-phase chemistry of the silaformyl anion, HSiO sup minus

Journal Article · Wed Jan 31 00:00:00 EST 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00159a016· OSTI ID:6946500

Gronert, S; Prodnuk, S; DePuy, C H ^[1]; O'Hair, R A.J. ^[2]; Suelzle, D ^[3]; Damrauer, R ^[4]

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1. Univ. of Colorado, Boulder (USA)
2. Univ. of Adelaide (Australia)
3. Institut fuer Organische Chemie der Technischen Universitaet Berlin (West Germany)
4. Univ. of Colorado, Denver (USA)

The silaformyl anion, HSiO{sup {minus}}, has been prepared by collisionally induced dissociation (CID) of H{sub 3}SiO{sup {minus}} in a tandem flowing afterglow selected ion flow tube (FA-SIFT). The chemistry of the silaformyl anion has been studied in detail. Reactions with CO{sub 2}, COS, CS{sub 2}, SO{sub 2}, O{sub 2}, acetic acid, nitromethane, and hexafluorobenzene reveal a rich chemistry. For example, the sailaformyl anion reacts with CO{sub 2} by both an oxidative pathway giving HSiO{sub 2}{sup {minus}} and CO and a reductive path giving SiO and HCO{sub 2}{sup {minus}}. Typically, the silaformyl anion, which could have several sites of reactivity, behaves both as an oxygen nucleophile and as a hydride donor. Detailed mechanistic studies have been carried out on many of these reactions with isotopically labeled H{sup 29}SiO{sup {minus}} and HSi{sup 18}O{sup {minus}}. In addition to its reaction chemistry, the heat of formation of the silaformyl anion, its basicity, and the heat of formation of its parent compound have been estimated. Ab initio computations on the silaformyl anion have been carried out and demonstrate that HSiO{sup {minus}} is more than 40 kcal/mol more stable than HOSi{sup {minus}}.

• OSTI ID: 6946500
• Journal Information: Journal of the American Chemical Society; (USA), Vol. 112:3; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
SILICON COMPOUNDS
CHEMICAL REACTIONS
ACETIC ACID
CARBON MONOXIDE
DATA ANALYSIS
EXPERIMENTAL DATA
FORMATION HEAT
GAS ANALYSIS
MEASURING INSTRUMENTS
MEASURING METHODS
OXYGEN
SULFUR DIOXIDE
CARBON COMPOUNDS
CARBON OXIDES
CARBOXYLIC ACIDS
CHALCOGENIDES
DATA
ELEMENTS
ENTHALPY
INFORMATION
MONOCARBOXYLIC ACIDS
NONMETALS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
REACTION HEAT
SULFUR COMPOUNDS
SULFUR OXIDES
THERMODYNAMIC PROPERTIES
360603* - Materials- Properties
400201 - Chemical & Physicochemical Properties