请选择 进入手机版 | 继续访问电脑版
搞化学,就上化学吧!·有朋自远方来不亦乐乎?欢迎新人送金币,点击进入!·社区工具·最新主题
热爱我们的家园,分享我们的生活,畅想我们的未来。

☆麦兜☆

 找回密码
 加入我们

QQ登录

只需一步,快速开始

☆麦兜☆ 门户 文章 捷报 查看内容

Organometallics - Unconventional Facile Way to Metallanaphthalenes from Metal Indenyl Complexes Predicted by DFT Calculations: Origin of Their Different Thermodynamics and Tuning Their Kinetics by Substituents

2014-4-28 21:26| 发布者: Mcdull| 查看: 1882| 评论: 0|原作者: Metalcarbene|来自: 捷报频传

摘要: 3月10号投到OM,26号4个小修,一个不推荐发表。主编给了修的机会。4月7日返回修改稿,8号收,还算顺利。 内容主要是理论取代基的调节预测了一种反传统的合成金属萘的方法,并对取代基降低能垒的原因进行了分析。
Authors:
Jinglan Fan, Xuerui Wang, and Jun Zhu*

Journal: Organometallics

Year: 2014

FirstPage-LastPage: ASAP

Keywords:
reaction mechanisms
DFT
Metallanaphthalene
Metal Indenyl Complexes

TOC:
om-2014-00245q_0010.gif

Abstract:
Metallaaromatics have attracted considerable interest from both experimentalists and theoreticians over the past three decades. However, most studies in this field have focused on metallabenzene, in which a CH group is replaced by a transition metal fragment. In comparison with monocyclic metallabenzenes, bicyclic metallanaphthalenes are rather limited. Thus, it is urgent to explore more synthetic approaches to this less developed system. One of the difficulties in the synthesis of metallanaphthalenes could be due to its low thermodynamic stability relative to the metal indenyl complexes. Here we present a thorough theoretical investigation by quantum chemical calculations to explore the possibility of realizing traditionally “unstable” metallanaphthalenes by an isomerization of traditionally “stable” metal indenyl complexes. We systematically investigated how different substituent(s) at different position(s) on the metallacycle affect such a rearrangement. Our results indicate that although indenyl complexes are known to be thermally robust, it should be possible to shift the thermodynamic and kinetic balance toward the metallanaphthalene complexes by choosing proper ancillary substituents on the metallabicycle, which is in sharp contrast to the traditional facile isomerization of metallabenzenes to cyclopentadienyl (Cp) complexes. Therefore, our findings suggest a novel avenue to metallanaphthalenes.

投稿经历:3月10号投到OM,26号4个小修,一个不推荐发表。主编给了修的机会。4月7日返回修改稿,8号收,还算顺利。
内容主要是理论取代基的调节预测了一种反传统的合成金属萘的方法,并对取代基降低能垒的原因进行了分析。

http://pubs.acs.org/doi/abs/10.1021/om500245q
or
http://junzhu.chem8.org/node/59

有无问题,欢迎跟帖捧场。

相关分类

手机版|Archiver|chem8.org ( 闽ICP备17001654号 )  

闽公网安备 35020602000685号

GMT+8, 2017-5-25 12:32 , Processed in 0.074751 second(s), 24 queries .

Powered by Discuz! X2.5

© 2001-2012 Comsenz Inc.

回顶部