探究金属磷苯难以合成的根源:1,2-迁移变得相对容易
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- 英文论文题名：Probing the Origin of Challenge of Realizing Metallaphosphabenzenes:Unfavorable 1,2-Migration in Metallapyridines Becomes Feasible in Metallaphosphabenzenes
- 论文作者：吴晶晶 ; 郝玉蕾 ; 朱军
- 英文论文作者：Jingjing Wu ; Yulei Hao ; Jun Zhu ; Department of Chemistry ; Xiamen University
- 年：2016
- 作者机构：厦门大学化学系;
- 论文关键词：1 ; 2-迁移 ; 金属磷苯 ; 金属吡啶 ; 密度泛函理论
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十五分会：物理有机
- 语种：中文
- 分类号：O641.4
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十五分会 ; 物理有机
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：249k
- 原文格式：D
- 会议级别：全国
摘要
金属苯一直以来备受关注,然而金属磷苯在实验上却至今未有报道~([1])。因此,探究金属磷苯难以合成的根源就显得尤为重要。这里,我们尝试利用密度泛函理论探究这一问题。计算结果表明,1,2-迁移在金属吡啶环中不可行但却在金属磷苯中相对容易实现。这可以归因于P原子不愿意参与p键的形成。同时,p给体配体和5d过渡金属能够稳定金属磷苯。相较于氢和甲基的迁移,氯配体更易发生迁移~([2]),这可能是金属-磷双键的显著极化导致了较低的活化能垒。而一氧化碳配体能够降低迁移反应能垒可归因于一氧化碳能够削弱金属中心和磷原子的相互作用。这些发现为合成化学家实现第一例金属磷苯提供了有用信息。
Metallabenzenes have attracted considerable interest of both theoretical and experimental chemists. However, metallaphosphabenzenes has never been synthesized. Thus, understanding the origin of the synthetic challenge is particularly urgent for experimentalists. Now DFT calculations have been carried out to examine this issue. Our results reveal that the 1,2-migration in metallapyridines is unfavorable whereas such a 1,2-migration in metallaphosphabenzenes is feasible, which can be rationalized by the reluctance of phosphorus to participate in π bonding. In addition, π-donor ligands and the 5d transition metals can stabilize metallaphosphabenzenes. Compared with hydride and methyl migration, the chloride migration has a relatively lower activation barrier. CO ligand could further decrease the reaction barrier of the migration due to a weaker interaction between the metal centre and the phosphorus atom. All of these findings could help synthetic chemists to realize the first metallaphosphabenzene.
Metallabenzenes have attracted considerable interest of both theoretical and experimental chemists. However, metallaphosphabenzenes has never been synthesized. Thus, understanding the origin of the synthetic challenge is particularly urgent for experimentalists. Now DFT calculations have been carried out to examine this issue. Our results reveal that the 1,2-migration in metallapyridines is unfavorable whereas such a 1,2-migration in metallaphosphabenzenes is feasible, which can be rationalized by the reluctance of phosphorus to participate in π bonding. In addition, π-donor ligands and the 5d transition metals can stabilize metallaphosphabenzenes. Compared with hydride and methyl migration, the chloride migration has a relatively lower activation barrier. CO ligand could further decrease the reaction barrier of the migration due to a weaker interaction between the metal centre and the phosphorus atom. All of these findings could help synthetic chemists to realize the first metallaphosphabenzene.
引文
[1]Huang,C.;Hao,Y.;Zhao,Y.;Zhu,J.Organometallics 2014,33:817.
[2]Huang,Y.;Zhu,J.Chem.Asian J.2015,10:405.
[2]Huang,Y.;Zhu,J.Chem.Asian J.2015,10:405.