An a b i n i t i o study of the rearrangement of carbonyl compounds to oxacarbenes
- 1 January 1977
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 66 (1) , 298-302
- https://doi.org/10.1063/1.433623
Abstract
As the first part of a systematic theoretical study of oxacarbene rearrangement, ab initio SCF MO calculations employing a split valence shell basis set have been carried out for the model conversion of formaldehyde to the corresponding oxacarbene. The various cross‐sections of the reaction hypersurface were obtained by complete geometry optimization. The results suggest that, at least for the present model system, the reaction takes place preferentially in the first triplet (T1) state via a concerted pathway.Keywords
This publication has 10 references indexed in Scilit:
- Photochemical ring expansion of cyclic ketones via cyclic oxacarbenesAccounts of Chemical Research, 1975
- Intersystem crossing of triplet formaldehydeChemical Physics Letters, 1974
- Lifetimes of triplet formaldehydeChemical Physics Letters, 1974
- A Simple EH Model for the Photochemical Cyclobutanone‐Tetrahydrofurylidene IsomerizationAngewandte Chemie International Edition in English, 1974
- The Peculiar Behavior of Electronically Excited Cyclobutanones: A Photochemical Example of the Consequence of Through‐Bond InteractionAngewandte Chemie International Edition in English, 1974
- Theoretical studies of carbonyl photochemistry. I. ab initio potential energy surfaces for the photodissociation H2CO*→H + HCOChemical Physics Letters, 1972
- Photodecomposition of CH2O, CD2O, CHDO, and CH2O-CD2O mixtures at xenon flash lamp intensitiesJournal of the American Chemical Society, 1969
- A study of the primary processes in CH2O and CD2O photolysesJournal of the American Chemical Society, 1967
- Self-Consistent Orbitals for RadicalsThe Journal of Chemical Physics, 1954
- New Developments in Molecular Orbital TheoryReviews of Modern Physics, 1951