Interconversion of metallabenzenes and cyclic 畏2-allene- coordinated complexes

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	Interconversion of metallabenzenes and cyclic 畏2-allene- coordinated complexes
	Lin, Ran ; Zhao, Jing ; Chen, Hanyu ; Zhang, Hong ; Xia, Haiping ; 张弘 ; 夏海平
刊名	http://dx.doi.org/10.1002/asia.201200231
	2012
关键词	Coordination reactions Hydrocarbons Osmium
英文摘要	Treatment of the osmabenzene [Os{CHC(PPh3)CHC(PPh 3)CH} Cl2(PPh3)2]Cl (1) with excess 8-hydroxyquinoline produces monosubstituted osmabenzene [Os{CH C(PPh 3) CHC(PPh3)CH}(C9H6NO)Cl(PPh 3)]Cl (2) or disubstituted osmabenzene [Os{CHC(PPh 3)CHC(PPh3)CH} (C9H6NO) 2]Cl (3) under different reaction conditions. Osmabenzene 2 evolves into cyclic 畏2-allene-coordinated complex [Os{CH=C(PPh 3)CH=(畏2-C=CH2)}(C9H 6NO)(PPh3)2]Cl (4) in the presence of excess PPh3 and NaOH, presumably involving a P-C bond cleavage of the metallacycle. Reaction of 4 with excess 8-hydroxyquinoline under air affords the SNAr product [(C9H6NO)Os{CHC(PPh 3)CHCHC} (C9H6NO)(PPh3)]Cl (5). Complex 4 is fairly reactive to a nucleophile in the presence of acid, which could react with water to give carbonyl complex [Os{CH=C(PPh3)CH= CH2}(C9H6NO) (CO)(PPh3) 2]Cl (6). Complex 4 also reacts with PPh3 in the presence of acid and results in a transformation to [Os {CHC(PPh3)CHCHC} (C9H6NO)Cl (PPh3)2]Cl (7) and [Os{CH=C(PPh3) CH=(畏2-C=CH(PPh3))}(C 9H6NO) Cl(PPh3)]Cl (8). Further investigation shows that the ratio of 7 and 8 is highly dependent on the amount of the acid in the reaction. 漏 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
语种	英语
出版者	John Wiley and Sons Ltd
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/89570]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Lin, Ran,Zhao, Jing,Chen, Hanyu,等. Interconversion of metallabenzenes and cyclic 畏2-allene- coordinated complexes[J]. http://dx.doi.org/10.1002/asia.201200231,2012.
APA	Lin, Ran.,Zhao, Jing.,Chen, Hanyu.,Zhang, Hong.,Xia, Haiping.,...&夏海平.(2012).Interconversion of metallabenzenes and cyclic 畏2-allene- coordinated complexes.http://dx.doi.org/10.1002/asia.201200231.
MLA	Lin, Ran,et al."Interconversion of metallabenzenes and cyclic 畏2-allene- coordinated complexes".http://dx.doi.org/10.1002/asia.201200231 (2012).