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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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first_indexed 2017-03-27T12:57:27Z
last_indexed 2018-02-09T05:20:54Z
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spelling 2017-07-07T15:43:50.6669817 v2 32703 2017-03-27 Selective Functionalization of a Variety of Hydrocarbon C(sp3)–H Bonds Initiated by Cp*W(NO)(CH2CMe3)(η3-CH2CHCHPh) 28c45bbeeba294da7042950705b98e0a 0000-0002-4304-0243 Russell Wakeham Russell Wakeham true false 2017-03-27 EEN 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. Journal Article Organometallics 36 1 39 52 0276-7333 1520-6041 31 12 2017 2017-12-31 10.1021/acs.organomet.6b00739 COLLEGE NANME Engineering COLLEGE CODE EEN Swansea University 2017-07-07T15:43:50.6669817 2017-03-27T11:01:22.8939623 Faculty of Science and Engineering School of Engineering and Applied Sciences - Uncategorised Russell Wakeham 0000-0002-4304-0243 1 Rhett A. Baillie 2 Brian O. Patrick 3 Peter Legzdins 4 Devon C. Rosenfeld 5
title Selective Functionalization of a Variety of Hydrocarbon C(sp3)–H Bonds Initiated by Cp*W(NO)(CH2CMe3)(η3-CH2CHCHPh)
spellingShingle Selective Functionalization of a Variety of Hydrocarbon C(sp3)–H Bonds Initiated by Cp*W(NO)(CH2CMe3)(η3-CH2CHCHPh)
Russell Wakeham
title_short Selective Functionalization of a Variety of Hydrocarbon C(sp3)–H Bonds Initiated by Cp*W(NO)(CH2CMe3)(η3-CH2CHCHPh)
title_full Selective Functionalization of a Variety of Hydrocarbon C(sp3)–H Bonds Initiated by Cp*W(NO)(CH2CMe3)(η3-CH2CHCHPh)
title_fullStr Selective Functionalization of a Variety of Hydrocarbon C(sp3)–H Bonds Initiated by Cp*W(NO)(CH2CMe3)(η3-CH2CHCHPh)
title_full_unstemmed Selective Functionalization of a Variety of Hydrocarbon C(sp3)–H Bonds Initiated by Cp*W(NO)(CH2CMe3)(η3-CH2CHCHPh)
title_sort Selective Functionalization of a Variety of Hydrocarbon C(sp3)–H Bonds Initiated by Cp*W(NO)(CH2CMe3)(η3-CH2CHCHPh)
author_id_str_mv 28c45bbeeba294da7042950705b98e0a
author_id_fullname_str_mv 28c45bbeeba294da7042950705b98e0a_***_Russell Wakeham
author Russell Wakeham
author2 Russell Wakeham
Rhett A. Baillie
Brian O. Patrick
Peter Legzdins
Devon C. Rosenfeld
format Journal article
container_title Organometallics
container_volume 36
container_issue 1
container_start_page 39
publishDate 2017
institution Swansea University
issn 0276-7333
1520-6041
doi_str_mv 10.1021/acs.organomet.6b00739
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Uncategorised{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Uncategorised
document_store_str 0
active_str 0
description 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.
published_date 2017-12-31T03:40:10Z
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score 11.012678

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