Computations Offer an Unconventional Route to Metallaphosphabenzene from a Half-Phosphametallocene

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	Computations Offer an Unconventional Route to Metallaphosphabenzene from a Half-Phosphametallocene
	Huang, Chao ; Hao, Yulei ; Zhao, Yufen ; Zhu, Jun ; Zhao YF(赵玉芬) ; Zhu J(朱军)
刊名	http://dx.doi.org/10.1021/om401188v
	2014-02-10
关键词	CYCLOPENTADIENYL COMPLEXES METALLOAROMATIC COMPLEXES METALLABENZENE CHEMISTRY BORABENZENE DERIVATIVES CRYSTAL-STRUCTURE TRANSITION-METAL RING CURRENTS BASIS-SETS REACTIVITY AROMATICITY
英文摘要	Chinese National Natural Science Foundation [21103142, 21133007, 21232005]; National Basic Research Program of China [2011CB808504, 2012CB821600]; 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 continuing interest of both theoretical and experimental chemists since the first metallabenzene was predicted by Hoffmann and isolated by Roper. In sharp contrast to metallabenzenes, metallaphosphabenzene (MPB) is much less developed and has not been synthesized so far. Thus, developing synthetic approaches is urgent. Here we present thorough density functional theory (DFT) calculations on the thermodynamics and kinetics of the rearrangement between MPBs and the corresponding eta(5)-phosphacyclopentadiene (eta(5)-PCp) complexes. The effects of metal centers, ligands, and substituents on the metallacycles were examined systematically. Our results reveal that the third-row metal osmium has the highest possibility to form MPB in comparison with the first-row metal iron and second-row metal ruthenium. Substituents were found to have a significant effect on the thermodynamics and kinetics of the rearrangement reactions, leading to an interconversion between osrnaphosphabenzenes (OsPBs) and the corresponding eta(5)-PCp complexes by simply tuning the substituents on the metallacycles. Thus; all of these findings should invite experimentalists to test these unconventional methods to realize the first MPB.
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/2288/89388]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Huang, Chao,Hao, Yulei,Zhao, Yufen,et al. Computations Offer an Unconventional Route to Metallaphosphabenzene from a Half-Phosphametallocene[J]. http://dx.doi.org/10.1021/om401188v,2014.
APA	Huang, Chao,Hao, Yulei,Zhao, Yufen,Zhu, Jun,赵玉芬,&朱军.(2014).Computations Offer an Unconventional Route to Metallaphosphabenzene from a Half-Phosphametallocene.http://dx.doi.org/10.1021/om401188v.
MLA	Huang, Chao,et al."Computations Offer an Unconventional Route to Metallaphosphabenzene from a Half-Phosphametallocene".http://dx.doi.org/10.1021/om401188v (2014).