The Wolff rearrangement: The relevant portion of the oxirene-ketene potential energy hypersurface

Journal Article · Wed Nov 02 04:00:00 EST 1994 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00101a039· OSTI ID:7070228

Scott, A P; Nobes, R H; Radom, L ^[1]; Schaefer, III, H F ^[2]

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1. Australian National Univ., Canberra (Australia)
2. Univ. of Georgia, Athens, GA (United States)

The portion of the C[sub 2]H[sub 2]O potential energy hypersurface that includes oxirene, formylmethylene, and ketene has been studied with ab initio methods incorporating high levels of electron correlation and basis sets that include up to f and g functions. Our best geometries were determined at the CCSD(T)/6-3 UG(df,p) level of theory. Single-point energies were then determined by using CCSD(T) and BD(T) calculations with the cc-pVTZ basis set augmented with additional f and g polarization functions. Our main conclusion is that there is little or no barrier separating formylmethylene from oxirene, the potential energy surface linking these two species begin extremely flat. On the other hand, a more significant barrier (21-23 kJ mol[sup [minus]1]) separates formylmethylene or oxirene from ketene. These results strongly support the previously postulated intermediacy of oxirene in the Wolff rearrangement. Ketene is found to lie 325 kJ mol[sup [minus]1] lower in energy than oxirene. Our predicted energy threshold for the scrambling of carbon atoms in ketene (348 kJ mol[sup [minus]1]) is in close agreement with a recent experimental value (340 kJ mol[sup [minus]1]). 42 refs., 5 figs., 3 tabs.

• OSTI ID: 7070228
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 116:22; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
661300 -- Other Aspects of Physical Science-- (1992-)
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
99 GENERAL AND MISCELLANEOUS
990200 -- Mathematics & Computers
CALCULATION METHODS
CHEMICAL REACTIONS
COMPILED DATA
DATA
ENERGY
HARTREE-FOCK METHOD
INFORMATION
ISOMERIZATION
KETENES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
POTENTIAL ENERGY
THERMODYNAMICS