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

Russell Wakeham Orcid Logo, Rhett A. Baillie, Brian O. Patrick, Peter Legzdins, Devon C. Rosenfeld

Organometallics, Volume: 36, Issue: 1, Pages: 39 - 52

Swansea University Author: Russell Wakeham Orcid Logo

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DOI (Published version): 10.1021/acs.organomet.6b00739

Abstract

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 o...

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Published in: Organometallics
ISSN: 0276-7333 1520-6041
Published: 2017
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URI: https://cronfa.swan.ac.uk/Record/cronfa32703
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Abstract: 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.
College: Faculty of Science and Engineering
Issue: 1
Start Page: 39
End Page: 52

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