A theoretical study of the [4 + 4] dimerization of thioformylketene.
[reaction and structure: see text] A theoretical study (B3LYP and G3MP2B3) of the dimerization of thioformylketene (1) was performed. Four pathways-two [4 + 2] pathways with thioformylketene (1), one [4 + 4] pathway with 1, and one [4 + 2] pathway involving 1 and thietone (11)-were considered. Interestingly, the [4 + 4] pathway with 1 had the lowest barrier (3.8 kcal/mol). The geometry of the transition state TS14 is unusual, with the forming bonds in the plane of the ketene. This suggests that the reaction is pseudopericyclic.
Sadasivam
Dhandapani V
DV
Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA.
Birney
David M
DM