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Ortho-selective C-Hactivation of substituted benzenes effected by a tungsten alkylidene complex without substituent coordination

TitleOrtho-selective C-Hactivation of substituted benzenes effected by a tungsten alkylidene complex without substituent coordination
Publication TypeJournal Article
Year of Publication2006
AuthorsTsang, JYK, Buschhaus, MSA, Legzdins, P, Patrick, BO
JournalOrganometallics
Volume25
Pagination4215-4225
Date PublishedAug
Type of ArticleArticle
ISBN Number0276-7333
KeywordsCLEAVAGE, CRYSTAL-STRUCTURE, ELIMINATION, H BONDS, IRIDIUM, MECHANISM, METAL-COMPLEXES, {ARYL
Abstract

{Gentle thermolysis of the bis(neopentyl) complex Cp*W(NO)(CH2CMe3)(2) (1) at 70 degrees C in various substituted benzenes results in the loss of neopentane and the generation of the transient alkylidene complex Cp*W(NO)(=CHCMe3) (A), which subsequently effects single C-H bond activations of the benzenes. These activations exhibit a pronounced selectivity for the C-H linkages ortho to the benzene substituents. Thus, thermal reactions of 1 with C6H5X lead to the preferential formation of the corresponding Cp*W( NO)(CH2CMe3)(o-C6H4X) complexes, the ortho-selectivity, i. e.

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