Selective Functionalization of a Variety of Hydrocarbon C(sp3)–H Bonds Initiated by Cp*W(NO)(CH2CMe3)(η3-CH2CHCHPh)

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• 作者：Russell J. Wakeham ; Rhett A. Baillie ; Brian O. Patrick ; Peter LegzdinsDevon C. Rosenfeld
• 刊名：Organometallics
• 出版年：2017
• 出版时间：January 9, 2017
• 年：2017
• 卷：36
• 期：1
• 页码：39-52
• 全文大小：750K
• ISSN：1520-6041

文摘

Cp*W(NO)(CH₂CMe₃)(η³-CH₂CHCHPh) (1) effects C(sp³)–H activations of methane, ethane, propane, and n-butane exclusively at their terminal carbons and forms the corresponding Cp*W(NO)(alkyl)(η³-CH₂CHCHPh) complexes. It also activates (n-Bu)₂O, 1-chloropropane, and Me₄Si in a similar manner. Exposure of the Cp*W(NO)(alkyl)(η³-CH₂CHCHPh) complexes to carbon monoxide results in initial 1,1-CO insertion into the newly formed tungsten–alkyl bonds and formation of the corresponding η¹-acyl complexes, some of which can be isolated. Additional functionalization of the C–H activation products occurs upon exposure to CO under more forcing conditions. Such treatment produces η²-bound unsaturated-ketone complexes resulting from CO insertion into the W–alkyl σ bonds followed by cross-coupling of the η¹-acyl and the η³-allyl ligands and coordination of CO at the resulting vacant coordination site at tungsten. The unsaturated ketones can be released from the metal’s coordination spheres either by photolysis of the complexes in MeCN or by further exposure of them to CO. All new compounds have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of six of them have been established by single-crystal X-ray crystallographic analyses.