Generalized valence bond description of simple ylides

Journal Article · Sat Jan 01 04:00:00 EST 1983 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00362a001· OSTI ID:5622594

Dixon, D A; Dunning, Jr, T H; Eades, R A; Gassman, P G

The electronic structures of the simplest ylides of nitrogen, oxygen, phosphorus, and sulfur have been determined from ab initio molecular orbital theory at the generalized valence bond (GVB) + POL-CI level. The calculations were performed with double-zeta quality basis sets augmented by polarization (d) functions on the heavy atoms and a set of diffuse s and p functions on carbon. The energies for the internal proton-transfer reaction to form the ylide from its most stable isomer, CH/sub 3/XH/sub n/ ..-->.. CH/sub 2//sup -/XH/sub n+1//sup +/, are 52.5, 66.3, 82.9, and 92.8 kcal/mol for X = P, N, S, and O, respectively, at the GVB + Pol-CI level. GVB orbitals for CH/sub 3/NH/sub 2/, CH/sub 3/OH, CH/sub 3/PH/sub 2/, and CH/sub 3/SH are presented. Differences in bonding, specifically for the lone pairs, between first- and second-row elements are discussed. The GVB orbitals for the ylides are discussed and are employed in a description of the bonding in these species. 30 references, 11 figures, 2 tables.

• Research Organization: Argonne National Lab., IL
• OSTI ID: 5622594
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 105:24; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALCOHOLS
AMINES
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
CONFIGURATION INTERACTION
CORRELATIONS
DOCUMENT TYPES
ELECTRONIC STRUCTURE
EXTRAPOLATION
HYDROXY COMPOUNDS
ISOMERIZATION
MATHEMATICAL MODELS
MATHEMATICS
METHANOL
METHYLAMINE
MOLECULAR ORBITAL METHOD
MOLECULAR STRUCTURE
NUMERICAL ANALYSIS
NUMERICAL SOLUTION
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
REACTION INTERMEDIATES
REVIEWS
THIOLS
VALENCE