TY - JOUR
T1 - Trimethylenemethane dianion and the controversial notion of “y-aromaticity”
AU - Agranat, Israel
AU - Skancke, Anne
PY - 1985/2
Y1 - 1985/2
N2 - The Y-shaped trimethylenemethane dianion (TMM2-) has been studied by RHF ab initio calculations at the 6-31G level. The planar D3h form was found to be the most stable conformation. The barriers for 1, 2, and 3 rotations were found to be 21.7, 60.6, and 159.4 kcal/mol, respectively. Moreover, the planar D3hTMM2-form was found to be more stable than the isoelectronic, linearly delocalized butadiene dianions by about 30 kcal/mol. The alternation of charges (as calculated on the basis of Mulliken population analysis) was found to be more pronounced than in related systems. The notion of the Y-aromaticity is considered and vitalized on the basis of these data. The unstable character of the triply rotated TMM2- was found to be appropriately termed “Möbius antiaromaticity” since the destabilizing delocalization is pericyclic.
AB - The Y-shaped trimethylenemethane dianion (TMM2-) has been studied by RHF ab initio calculations at the 6-31G level. The planar D3h form was found to be the most stable conformation. The barriers for 1, 2, and 3 rotations were found to be 21.7, 60.6, and 159.4 kcal/mol, respectively. Moreover, the planar D3hTMM2-form was found to be more stable than the isoelectronic, linearly delocalized butadiene dianions by about 30 kcal/mol. The alternation of charges (as calculated on the basis of Mulliken population analysis) was found to be more pronounced than in related systems. The notion of the Y-aromaticity is considered and vitalized on the basis of these data. The unstable character of the triply rotated TMM2- was found to be appropriately termed “Möbius antiaromaticity” since the destabilizing delocalization is pericyclic.
UR - http://www.scopus.com/inward/record.url?scp=0003163532&partnerID=8YFLogxK
U2 - 10.1021/ja00290a023
DO - 10.1021/ja00290a023
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
AN - SCOPUS:0003163532
SN - 0002-7863
VL - 107
SP - 867
EP - 871
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 4
ER -