Structures of 1-(arylseleninyl)naphthalenes:: O, G, and Y dependences in 8-G-1-[p-YC6H4Se(O)]C10H6
Structures of 1-(arylseleninyl)naphthalenes:: O, G, and Y dependences in 8-G-1-[p-YC6H4Se(O)]C10H6
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DOI：
10.1021/jo060527f
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发表时间：
2006-07-21
影响因子：
3.6
通讯作者：
Nakanishi, Waro
中科院分区：
文献类型：
--
作者：
Hayashi, Satoko;Wada, Hideki;Nakanishi, Waro
本文用X射线晶体学方法研究了8- G- 1-[p-YC_6 H_4Se（O）] C_（10）H_6 [1（G = H），2（G）F），3（G）Cl），4（G）Br）：Y）H，OMe，OCH_2 Ph，t-Bu，Me，Cl，和NO_2]和（1-C_（10）H_7）（2）SeO（5）的晶体结构. 1的结构均为A（1（A）），其中Se-C-Ar键和Se-O键分别垂直于和平行于萘基平面。2-4的那些也是A。由于8- G- 1-（p-YC_6 H_4Se）C_（10）H_6 [ 7（G）F）、8（G）Cl）和9（G）Br）]的结构都是B，结果表明，随着O原子的引入，7-9的B急剧变化为2- 4的A。由O决定1- 4的A结构的因素称为O依赖性。O依赖性的起源是非键的n（p）（O）-π（Nap）相互作用，这导致CT从np（O）到d（Nap），因为1- 4中的O由于极性Se+）O-键而高度富电子，并且d（Nap）充当受体。如果Se-O键的方向和d（Nap）的p轨道的方向分别取x轴和z轴，则n（p）（O）有两种类型，npy（O）和n（pz）（O）. 5中的双重但独立的n（p）（O）- - - pi（Nap）相互作用导致5（AA）。1中的p-YC 6 H4 Se基团的构象根据Y而变化（Y依赖性），尽管效果不强。的Y依赖性解释的基础上的CT的大小的np（O）f-d（Ar）型1，除了np（O）- pi（Nap）相互作用。如果p-YC_6 H_4Se基团的接受能力与萘基类似，则1中SedO基团周围的结构接近于5（AA）的结构。2- 4的A通过np（G）-σ *（Se-O）3c-4 e相互作用进一步稳定，这被称为G依赖性。对1- 4（分别为11- 14）的甲基类似物进行的QC计算再现了观察到的结构，支持上述讨论，并揭示了能量分布。如果Br和Se之间的空间排斥包含在G依赖性中，O依赖性的能量降低效应将接近14中非键n（Br）-σ *（Se-O）3c-4 e相互作用的G依赖性.该值大致预测为20 kJ mol- 1。1- 5的结构很好地解释了O，G和Y的依赖性。
Structures of 8- G- 1-[ p- YC6H4Se(O)]C10H6 [1 ( G = H), 2 ( G) F), 3 ( G) Cl), and 4 ( G) Br): Y) H, OMe, OCH2Ph, t- Bu, Me, Cl, and NO2] and (1- C10H7)(2)SeO (5) are investigated by the X- ray crystallographic analysis. Structures of 1 are all A with regard to the naphthyl group ( 1 ( A)), where the Se-C-Ar and Se-O bonds are perpendicular to and parallel to the naphthyl plane, respectively. Those of 2-4 are also A. Since structures of 8- G- 1-( p- YC6H4Se) C10H6 [ 7 ( G) F), 8 ( G) Cl), and 9 ( G) Br)] are all B, the results exhibit that B of 7-9 change dramatically to A of 2- 4 with the introduction of O atoms. The factor to determine the A structures of 1- 4 by O is called O dependence. The origin of the O dependence is the nonbonded n(p)( O)- - - pi( Nap) interaction, which results in CT from np( O) to d( Nap) since O in 1- 4 is highly electron rich due to the polar Se+) O- bond and d( Nap) acts as an acceptor. There are two types of n(p)( O)' s, npy( O) and n(pz)( O), if the directions of the Se- O bond and the p- orbitals of d( Nap) are taken in the x- and z- axes, respectively. Double but independent n(p)( O)- - - pi( Nap) interactions in 5 lead to 5 ( AA). The conformation of the p- YC6H4Se group in 1 changes depending on Y ( Y dependence), although the effect is not strong. The Y dependence is explained on the basis of the magnitude of CT of the np( O) f d( Ar) type in 1, in addition to the np( O)- - - pi( Nap) interaction. The structure around the SedO group in 1 is close to that of 5 ( AA), if the accepting ability of the p- YC6H4Se group is similar to that of the naphthyl group. A of 2- 4 are further stabilized by the np( G)- - - sigma*( Se- O) 3c- 4e interactions, which are called G dependence. QC calculations performed on the methyl analogues of 1- 4 ( 11- 14, respectively) reproduced the observed structures, supported the above discussion, and revealed the energy profiles. The energy- lowering effect of the O dependence would be close to the G dependence of the nonbonded n( Br)- - - sigma*( Se-O) 3c- 4e interaction in 14 if the steric repulsion between Br and Se is contained in the G dependence. The value is roughly predicted as 20 kJ mol- 1. The structures of 1- 5 are well explained by O, G, and Y dependences.