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Ab Initio Study of Complexes with Two Cations as N−H Donors to F-: Structures and Spin−Spin Coupling Constants across N−H−F Hydrogen Bonds
journal contribution
posted on 2005-12-01, 00:00 authored by Janet E. Del Bene, José ElgueroA systematic ab initio study has been carried out to determine the MP2/6-31+G(d,p) structures and EOM-CCSD coupling constants across N−H−F−H−N hydrogen bonds for a series of complexes F(H3NH)2+,
F(HNNH2)2+, F(H2CNH2)2+, F(HCNH)2+, and F(FCNH)2+. These complexes have hydrogen bonds with two
equivalent N−H donors to F-. As the basicity of the nitrogen donor decreases, the N−H distance increases
and the N−H−F−H−N arrangement changes from linear to bent. As these changes occur and the hydrogen
bonds between the ion pairs acquire increased proton-shared character, 2hJF-N increases in absolute value and
1hJH-F changes sign. F(H3NH)2+ complexes were also optimized as a function of the N−H distance. As this
distance increases and the N−H···F hydrogen bonds change from ion-pair to proton-shared to traditional
F−H···N hydrogen bonds, 2hJF-N initially increases and then decreases in absolute value, 1JN-H decreases in
absolute value, and 1hJH-F changes sign. The signs and magnitudes of these coupling constants computed for
F(H3NH)2+ at short N−H distances are in agreement with the experimental signs and magnitudes determined
for the F(collidineH)2+ complex in solution. However, even when the N−H and F−H distances are taken
from the optimized structure of F(collidineH)2+, 2hJF-N and 1hJH-F are still too large relative to experiment.
When the distances extracted from the experimental NMR data are used, there is excellent agreement between
computed and experimental coupling constants. This suggests that the N−H−F hydrogen bonds in the isolated
gas-phase F(collidineH)2+ complex have too much proton-shared character relative to those that exist in solution.