m-Metallaphenol: Synthesis and Reactivity Studies

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	m-Metallaphenol: Synthesis and Reactivity Studies
	Han, Feifei ; Wang, Tongdao ; Li, Jinhua ; Zhang, Hong ; Xia, Haiping ; Zhang H(张弘) ; Xia HP(夏海平)
刊名	http://dx.doi.org/10.1002/chem.201304957
	2014-04-07
关键词	ELECTROPHILIC SUBSTITUTION-REACTIONS NUCLEOPHILIC AROMATIC-SUBSTITUTION CRYSTAL-STRUCTURE TRANSITION-METAL METALLABENZENES CHEMISTRY COMPLEX OSMABENZENE DENSITY METALLACYCLES
英文摘要	973 Program [2012CB821600]; National Natural Science Foundation of China [21174115, 21272193, 21332002]; Natural Science Foundation of Fujian Province [2011J05031]; Treatment of the osmium complex [Os{CHC-(PPh3)CH(OH)-(2)-CCH}(PPh3)(2)(NCS)(2)] (1) with excess triethylamine produces the first m-metallaphenol complex [Os{CHC(PPh3)CHC(OH)CH}(PPh3)(2)(NCS)(2)] (2). The NMR spectroscopic and structural data as well as the nucleus-independent chemical-shift (NICS) values suggest that osmaphenol 2 has aromatic character. The reactivity studies demonstrate that 2 can react with different isocyanates to form the annulation reaction products [Os{CHC(PPh3)CHC(OCONR)C}(PPh3)(2)(NCS)(2)] (R=Ph (3), iPr (7), Bn (8)) via the carbamate intermediates [Os{CHC(PPh3)CHC(O-CONHR)CH}(PPh3)(2)(NCS)(2)] (R=Ph (4), iPr (5), Bn (6)). In addition, the similar annulation reactions can be extended to other unsaturated compounds containing N-C multiple bonds, for example, isothiocyanates, pyridine, and sodium thiocyanate, which can produce the corresponding fused osmabenzene complexes. In contrast, the reactions of 2 with common electrophiles, such as NOBF4, NO2BF4, N-bromosuccinimide, and N-chlorosuccinimide only led to the decomposition of the metallaphenol ring. The experimental results suggest that 2 is very electrophilic and readily reacts with nucleophiles, which is mainly due to the metal center and the strong electron-withdrawing phosphonium group.
语种	英语
出版者	WILEY-V C H VERLAG GMBH
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/89329]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Han, Feifei,Wang, Tongdao,Li, Jinhua,et al. m-Metallaphenol: Synthesis and Reactivity Studies[J]. http://dx.doi.org/10.1002/chem.201304957,2014.
APA	Han, Feifei.,Wang, Tongdao.,Li, Jinhua.,Zhang, Hong.,Xia, Haiping.,...&夏海平.(2014).m-Metallaphenol: Synthesis and Reactivity Studies.http://dx.doi.org/10.1002/chem.201304957.
MLA	Han, Feifei,et al."m-Metallaphenol: Synthesis and Reactivity Studies".http://dx.doi.org/10.1002/chem.201304957 (2014).