TY - JOUR
T1 - When does electronic delocalization become a driving force of chemical bonding?
AU - Shaik, Sason S.
AU - Hiberty, Philippe C.
AU - Ohanessian, Gilles
AU - Lefour, Jean Michel
PY - 1988
Y1 - 1988
N2 - A curve-crossing diagram model is used to conceptualize the stability trends in delocalized clusters Xnz (n = 3, 4, 6; z = 0, -1; X = H, Li, Na, K, F, Cl, Br, I). The size of the diagram's gap (G) appears to be the decisive stability factor. Large gaps result in unstable (distortive) clusters with a high percentage of bond stretching and large quantum mechanical resonance energies (QMRE), e.g., H6. Since G is related to the strength of the two-center X-X bond it follows that only atoms which form very weak bonds will generate stable delocalized clusters. Such clusters will possess slightly stretched bonds (on a percentage basis) and small QMRE's (e.g., Li3,Li6). The strength of the π-bond between carbon atoms indicates that π-components, of conjugated π-σ-systems, are distortive. This is confirmed by ab initio σ-π energy partitions for benzene and allyl radical. The results show that the species involve distortive π-transition states which are forced to be delocalized by the σ-frames. In accord with the general trend, the distortive π-components also possess large QMRE. It is shown that the Hückel 4n/(4n + 2) dichotomy is reflected in the corresponding QMRE values but not in the π-distortivity, and that the connection between "aromaticity-antiaromaticity" and geometry is not necessary. These conclusions carry over to other σ-π-systems, Xn (X = CH, SiH, N, P; n = 4, 6). The QMRE and the π-distortivities are two distinct molecular properties which must be probed by different experiments. Measurements of rotational barriers (in allyl) and thermochemical resonance energies are shown to be QMRE-related properties. Measurements of the π-distortivity are rare.
AB - A curve-crossing diagram model is used to conceptualize the stability trends in delocalized clusters Xnz (n = 3, 4, 6; z = 0, -1; X = H, Li, Na, K, F, Cl, Br, I). The size of the diagram's gap (G) appears to be the decisive stability factor. Large gaps result in unstable (distortive) clusters with a high percentage of bond stretching and large quantum mechanical resonance energies (QMRE), e.g., H6. Since G is related to the strength of the two-center X-X bond it follows that only atoms which form very weak bonds will generate stable delocalized clusters. Such clusters will possess slightly stretched bonds (on a percentage basis) and small QMRE's (e.g., Li3,Li6). The strength of the π-bond between carbon atoms indicates that π-components, of conjugated π-σ-systems, are distortive. This is confirmed by ab initio σ-π energy partitions for benzene and allyl radical. The results show that the species involve distortive π-transition states which are forced to be delocalized by the σ-frames. In accord with the general trend, the distortive π-components also possess large QMRE. It is shown that the Hückel 4n/(4n + 2) dichotomy is reflected in the corresponding QMRE values but not in the π-distortivity, and that the connection between "aromaticity-antiaromaticity" and geometry is not necessary. These conclusions carry over to other σ-π-systems, Xn (X = CH, SiH, N, P; n = 4, 6). The QMRE and the π-distortivities are two distinct molecular properties which must be probed by different experiments. Measurements of rotational barriers (in allyl) and thermochemical resonance energies are shown to be QMRE-related properties. Measurements of the π-distortivity are rare.
UR - http://www.scopus.com/inward/record.url?scp=0000903479&partnerID=8YFLogxK
U2 - 10.1021/j100329a008
DO - 10.1021/j100329a008
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AN - SCOPUS:0000903479
SN - 0022-3654
VL - 92
SP - 5086
EP - 5094
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
IS - 18
ER -