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

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	Unconventional Facile Way to Metallanaphthalenes from Metal Indenyl Complexes Predicted by DFT Calculations: Origin of Their Different Thermodynamics and Tuning Their Kinetics by Substituents
	Fan, Jinglan ; Wang, Xuerui ; Zhu, Jun ; Zhu J(朱军)
刊名	http://dx.doi.org/10.1021/om500245q
	2014-05-12
关键词	VALENCE ISOMERS STABLE RUTHENABENZENES RING SUBSTITUENTS TRANSITION-METAL BASIS-SET METALLABENZENES IRIDABENZENES REACTIVITY DENSITY ENERGY
英文摘要	Chinese National Natural Science Foundation [21172184]; National Basic Research Program of China [2011CB808504]; Program for New Century Excellent Talents in University [NCET-13-0511]; Program for Changjiang Scholars and Innovative Research Team in University; Fundamental Research Funds for the Central Universities [2012121021]; 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.
语种	英语
出版者	AMER CHEMICAL SOC
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/89302]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Fan, Jinglan,Wang, Xuerui,Zhu, Jun,et al. Unconventional Facile Way to Metallanaphthalenes from Metal Indenyl Complexes Predicted by DFT Calculations: Origin of Their Different Thermodynamics and Tuning Their Kinetics by Substituents[J]. http://dx.doi.org/10.1021/om500245q,2014.
APA	Fan, Jinglan,Wang, Xuerui,Zhu, Jun,&朱军.(2014).Unconventional Facile Way to Metallanaphthalenes from Metal Indenyl Complexes Predicted by DFT Calculations: Origin of Their Different Thermodynamics and Tuning Their Kinetics by Substituents.http://dx.doi.org/10.1021/om500245q.
MLA	Fan, Jinglan,et al."Unconventional Facile Way to Metallanaphthalenes from Metal Indenyl Complexes Predicted by DFT Calculations: Origin of Their Different Thermodynamics and Tuning Their Kinetics by Substituents".http://dx.doi.org/10.1021/om500245q (2014).