Structure of 1-(Arylselanyl)naphthalenes. 2. G Dependence in 8-G-1-(p-YC6H4Se)C10H6
Structure of 1-(Arylselanyl)naphthalenes. 2. G Dependence in 8-G-1-(p-YC6H4Se)C10H6
复制标题
1-(芳基硒基)萘的结构。
DOI：
10.1021/jo010380m
复制
发表时间：
2002
影响因子：
3.6
通讯作者：
S. Hayashi
中科院分区：
文献类型：
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作者：
W. Nakanishi;S. Hayashi
通过X射线晶体结构分析、核磁共振波谱以及从头算分子轨道计算，对8 - G - 1 - (对 - YC₆H₄Se)C₁₀H₆（1（G = Cl）和2（G = Br）：Y = H（a），OMe（b），Me（c），Cl（d），Br（e），COOEt（f）以及NO₂（g））的结构进行了研究。1和2中所有成员的结构被推断为B型，这与4d - g（4（g(n)），其中G = H）的A型结构形成鲜明对比。在8 - G - 1 - (对 - YC₆H₄Se)C₁₀H₆中，对 - YC₆H₄Se基团的Se - Ci键在A型中几乎垂直于萘基平面，而在B型中位于该平面上。1和2中8位的氯和溴取代极大地将4（g(n)）的A型结构转变为B型。非键合的G - - - Se - C 3c - 4e型相互作用必定有助于稳定B型结构。1和2中的B型结构也应该通过3c - 4e型相互作用比4中的相同结构更稳定：4b的结构在晶体中为B型，对于4c来说B型会更稳定，对于4a可能也是如此……
The structures of 8-G-1-(p-YC6H4Se)C10H6 (1 (G = Cl) and 2 (G = Br): Y = H (a), OMe (b), Me (c), Cl (d), Br (e), COOEt (f), and NO2 (g)) were investigated by X-ray crystallographic analysis, NMR spectroscopy, and ab initio MO calculations. The structures of all members in 1 and 2 are concluded to be type B, which is in striking contrast to the type A structure for 4d−g (4 (g(n)), where G = H). The Se−Ci bond of the p-YC6H4Se group in 8-G-1-(p-YC6H4Se)C10H6 is almost perpendicular to the naphthyl plane in type A, and it is located on the plane in type B. The chlorine and bromine substitution at the 8-position in 1 and 2 dramatically changes the type A structure of 4 (g(n)) to type B. The nonbonded G- - -Se−C 3c-4e type interaction must contribute to stabilize the type B structure. The type B structure in 1 and 2 should also be more stabilized than the same structure in 4 by the 3c-4e type interaction: The structure of 4b is type B in the crystals and type B would be more stable for 4c and might be for 4a...