Summary: | 碩士 === 國立成功大學 === 化學系專班 === 94 === Weinhold and co-workers suggested 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. One is n(Y)→σ*(X-H) hyperconjugative interaction leading to X-H bond lengthening, and the other is rehybridization leading to X-H bond shortening. We concentrate on the C-H bond length of methane substituted by halogens. All computations are performed using Gaussian98 program, and all discussions in this paper are based on B3LYP/6-31+G* calculations.
Without hydrogen bond acceptors, the C-H bond length is mainly affected by s-character of C atom. When hydrogen bond acceptor is present, at larger distance, the C-H bond length shortening is due to the increase in the s-character of the C-H bond, and at shorter distance, the C-H bond length lengthening is due to n(Y)→σ*(X-H) hyperconjugative interaction. If we change with different hydrogen bond acceptors(Y), the C-H bond length is mainly affected by hyperconjugative interaction. The C-H bond length even has linear relation with E(2). If we use the same hydrogen bond acceptor(Y), the C-H bond length keeps the same in spite of different substitutions on C atom of methane. If we change the central atom, the C-H bond length still has linear relation with E(2), but the slope is different. The larger electronegativity of the central atom is, the smaller the slope is.
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