期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 125, 期 19, 页码 5973-5987出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja034656e
关键词
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The X-H bond length in X-H..Y hydrogen bonded complexes is controlled by a balance of two main factors acting in opposite directions. X-H bond lengthening due to n(Y)-->sigma*(H-X) hyperconjugative interaction is balanced by X-H bond shortening due to increase in the s-character and polarization of the X-H bond. When hyperconjugation dominates, X-H bond elongation is reflected in a concomitant red shift of the corresponding IR stretching frequency. When the hyperconjugative interaction is weak and the X-hybrid orbital in the X-H bond is able to undergo a sufficient change in hybridization and polarization, rehybridization dominates leading to a shortening of the X-H bond and a blue shift in the X-H stretching frequency.
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