TY - JOUR
T1 - A Theoretical Treatment of Nucleophilic Reactivity in Additions to Carbonyl Compounds. Role of the Vertical Ionization Energy
AU - Buncel, Erwin
AU - Um, Ik Hwan
AU - Wolfe, Saul
AU - Shaik, Sason S.
PY - 1988/2/1
Y1 - 1988/2/1
N2 - In water solvent, experimental ΔG* values for attack of X:− upon several esters correlate with the vertical ionization potentials of X:-.Two kinds of nucleophiles are discerned in this way, delocalized nucleophiles (AcO−, N3−, NO2−, etc.) exhibiting a larger slope than localized nucleophiles (F−, HO−, CH3O−, etc.). In terms of the state correlation diagram model, the existence of a ΔG* versus IP(X−)* correlation implies that an important aspect of the activation process is the single electron switch from X:− to the substrate that occurs during the nucleophilic attack.
AB - In water solvent, experimental ΔG* values for attack of X:− upon several esters correlate with the vertical ionization potentials of X:-.Two kinds of nucleophiles are discerned in this way, delocalized nucleophiles (AcO−, N3−, NO2−, etc.) exhibiting a larger slope than localized nucleophiles (F−, HO−, CH3O−, etc.). In terms of the state correlation diagram model, the existence of a ΔG* versus IP(X−)* correlation implies that an important aspect of the activation process is the single electron switch from X:− to the substrate that occurs during the nucleophilic attack.
UR - http://www.scopus.com/inward/record.url?scp=0001438402&partnerID=8YFLogxK
U2 - 10.1021/ja00212a041
DO - 10.1021/ja00212a041
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AN - SCOPUS:0001438402
SN - 0002-7863
VL - 110
SP - 1275
EP - 1279
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 4
ER -