Attractive Interaction Caused by the Linear F···Se−C Alignment in Naphthalene Peri Positions
Attractive Interaction Caused by the Linear F···Se−C Alignment in Naphthalene Peri Positions
复制标题
萘近位线性 F·Se−C 排列引起的吸引相互作用
DOI：
10.1021/ja974070q
复制
发表时间：
1998
影响因子：
15
通讯作者：
Y. Kawada
中科院分区：
文献类型：
--
作者：
W. Nakanishi;S. Hayashi;A. Sakaue;G. Ono;Y. Kawada
对8 - 氟 - 1 -（对茴香基硒基）萘（1）的X射线晶体学分析表明，F和Se原子以及对茴香基的本位碳（C(An)）呈线性排列。F原子和Se - C(An)键位于萘基平面上：F和Se原子之间的非键距为2.753(3) Å，FSeC(An)角为175.0(1)°。对1的模型化合物HF···SeH₂（其中1的芳基被氢取代）进行了6 - 311++G(3df,2pd)基组的从头算分子轨道计算。计算表明，当F、Se和C(An)原子呈线性排列时能量最低。基于自然布居分析，推测在HF···SeH₂形成过程中发生了从F到SeH₂的电荷转移，这支持了npx(F) - σ*(Se - C(An))相互作用。
The X-ray crystallographic analysis of 8-fluoro-1-(p-anisylselanyl)naphthalene (1) revealed that the F and Se atoms and the ipso-carbon of the p-anisyl group (C(An)) aligned linearly. The F atom and the Se−C(An) bond lay on the naphthyl plane: the nonbonded distance between F and Se atoms was 2.753(3) A and the FSeC(An) angle was 175.0(1)°. Ab initio MO calculations with the 6-311++G(3df,2pd) basis sets performed on the model compound of 1, HF···SeH2, where the aryl groups of 1 were replaced by hydrogens. The calculations exhibited that the energy minimum was achieved when the F, Se, and C(An) atoms aligned linearly. Charge transfer in the formation of HF···SeH2 was suggested to occur from F to SeH2 on the basis of natural population analysis, which supported the npx(F)−σ*(Se−C(An)) interaction.