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Thermal Chemistry of Cp*W(NO)(H)(η3-allyl) Complexes

R. Baillie, R. Wakeham, G. Lefèvre, A. Béthegnies, B. Patrick, P. Legzdins, D. Rosenfeld, Russell Wakeham Orcid Logo

Organometallics, Volume: 34, Issue: 13, Pages: 3428 - 3441

Swansea University Author: Russell Wakeham Orcid Logo

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DOI (Published version): 10.1021/acs.organomet.5b00426

Abstract

The thermal properties of Cp*W(NO)(H)(η3-CH2CHCMe2) (1), Cp*W(NO)(H)(η3-CH2CHCHPh) (2), and Cp*W(NO)(H)(η3-CH2CHCHMe) (3) (Cp* = η5-C5Me5) have been investigated. Thermolyses of 1–3 in n-pentane lead to the loss of the original allyl ligand and the formation of the same mixture of isomeric products,...

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Published in: Organometallics
ISSN: 0276-7333 1520-6041
Published: American Chemical Society (ACS) 2015
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URI: https://cronfa.swan.ac.uk/Record/cronfa32709
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fullrecord <?xml version="1.0"?><rfc1807><datestamp>2017-03-28T10:59:11.4036476</datestamp><bib-version>v2</bib-version><id>32709</id><entry>2017-03-27</entry><title>Thermal Chemistry of Cp*W(NO)(H)(&#x3B7;3-allyl) Complexes</title><swanseaauthors><author><sid>28c45bbeeba294da7042950705b98e0a</sid><ORCID>0000-0002-4304-0243</ORCID><firstname>Russell</firstname><surname>Wakeham</surname><name>Russell Wakeham</name><active>true</active><ethesisStudent>false</ethesisStudent></author></swanseaauthors><date>2017-03-27</date><deptcode>EEN</deptcode><abstract>The thermal properties of Cp*W(NO)(H)(&#x3B7;3-CH2CHCMe2) (1), Cp*W(NO)(H)(&#x3B7;3-CH2CHCHPh) (2), and Cp*W(NO)(H)(&#x3B7;3-CH2CHCHMe) (3) (Cp* = &#x3B7;5-C5Me5) have been investigated. Thermolyses of 1&#x2013;3 in n-pentane lead to the loss of the original allyl ligand and the formation of the same mixture of isomeric products, namely, Cp*W(NO)(H)(&#x3B7;3-CH2CHCHEt) (4a) and Cp*W(NO)(H)(&#x3B7;3-MeCHCHCHMe) (4b) and their coordination isomers. Similarly, 1 reacts with cyclohexane and n-heptane to form Cp*W(NO)(H)(&#x3B7;3-C6H9) and isomers of Cp*W(NO)(H)(&#x3B7;3-C7H13), respectively. It is likely that complexes 1&#x2013;3 first effect the selective, single-terminal C&#x2013;H activation of the linear alkanes, but the first-formed products are thermally unstable and undergo two additional successive C&#x2013;H activations to form the final allyl complexes. Consistent with this view is the fact that a bis(alkyl) intermediate complex can be trapped with N-methylmorpholine. Thus, the thermolysis of 1 in N-methylmorpholine affords a single organometallic complex, Cp*W(NO)(&#x3B7;2-CH2NC4H8O)(&#x3B7;1-CH2CH2CHMe2) (7). Complexes 2 and 3 react with N-methylmorpholine in an identical manner. Finally, 1 effects the multiple C&#x2013;H activations of 1-chloropropane and 1-chlorobutane and forms the corresponding Cp*W(NO)(Cl)(&#x3B7;3-allyl) complexes. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.</abstract><type>Journal Article</type><journal>Organometallics</journal><volume>34</volume><journalNumber>13</journalNumber><paginationStart>3428</paginationStart><paginationEnd>3441</paginationEnd><publisher>American Chemical Society (ACS)</publisher><issnPrint>0276-7333</issnPrint><issnElectronic>1520-6041</issnElectronic><keywords/><publishedDay>31</publishedDay><publishedMonth>7</publishedMonth><publishedYear>2015</publishedYear><publishedDate>2015-07-31</publishedDate><doi>10.1021/acs.organomet.5b00426</doi><url/><notes/><college>COLLEGE NANME</college><department>Engineering</department><CollegeCode>COLLEGE CODE</CollegeCode><DepartmentCode>EEN</DepartmentCode><institution>Swansea University</institution><apcterm/><lastEdited>2017-03-28T10:59:11.4036476</lastEdited><Created>2017-03-27T11:03:23.5300778</Created><path><level id="1">Faculty of Science and Engineering</level><level id="2">School of Engineering and Applied Sciences - Uncategorised</level></path><authors><author><firstname>R.</firstname><surname>Baillie</surname><order>1</order></author><author><firstname>R.</firstname><surname>Wakeham</surname><order>2</order></author><author><firstname>G.</firstname><surname>Lef&#xE8;vre</surname><order>3</order></author><author><firstname>A.</firstname><surname>B&#xE9;thegnies</surname><order>4</order></author><author><firstname>B.</firstname><surname>Patrick</surname><order>5</order></author><author><firstname>P.</firstname><surname>Legzdins</surname><order>6</order></author><author><firstname>D.</firstname><surname>Rosenfeld</surname><order>7</order></author><author><firstname>Russell</firstname><surname>Wakeham</surname><orcid>0000-0002-4304-0243</orcid><order>8</order></author></authors><documents/><OutputDurs/></rfc1807>
spelling 2017-03-28T10:59:11.4036476 v2 32709 2017-03-27 Thermal Chemistry of Cp*W(NO)(H)(η3-allyl) Complexes 28c45bbeeba294da7042950705b98e0a 0000-0002-4304-0243 Russell Wakeham Russell Wakeham true false 2017-03-27 EEN The thermal properties of Cp*W(NO)(H)(η3-CH2CHCMe2) (1), Cp*W(NO)(H)(η3-CH2CHCHPh) (2), and Cp*W(NO)(H)(η3-CH2CHCHMe) (3) (Cp* = η5-C5Me5) have been investigated. Thermolyses of 1–3 in n-pentane lead to the loss of the original allyl ligand and the formation of the same mixture of isomeric products, namely, Cp*W(NO)(H)(η3-CH2CHCHEt) (4a) and Cp*W(NO)(H)(η3-MeCHCHCHMe) (4b) and their coordination isomers. Similarly, 1 reacts with cyclohexane and n-heptane to form Cp*W(NO)(H)(η3-C6H9) and isomers of Cp*W(NO)(H)(η3-C7H13), respectively. It is likely that complexes 1–3 first effect the selective, single-terminal C–H activation of the linear alkanes, but the first-formed products are thermally unstable and undergo two additional successive C–H activations to form the final allyl complexes. Consistent with this view is the fact that a bis(alkyl) intermediate complex can be trapped with N-methylmorpholine. Thus, the thermolysis of 1 in N-methylmorpholine affords a single organometallic complex, Cp*W(NO)(η2-CH2NC4H8O)(η1-CH2CH2CHMe2) (7). Complexes 2 and 3 react with N-methylmorpholine in an identical manner. Finally, 1 effects the multiple C–H activations of 1-chloropropane and 1-chlorobutane and forms the corresponding Cp*W(NO)(Cl)(η3-allyl) complexes. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses. Journal Article Organometallics 34 13 3428 3441 American Chemical Society (ACS) 0276-7333 1520-6041 31 7 2015 2015-07-31 10.1021/acs.organomet.5b00426 COLLEGE NANME Engineering COLLEGE CODE EEN Swansea University 2017-03-28T10:59:11.4036476 2017-03-27T11:03:23.5300778 Faculty of Science and Engineering School of Engineering and Applied Sciences - Uncategorised R. Baillie 1 R. Wakeham 2 G. Lefèvre 3 A. Béthegnies 4 B. Patrick 5 P. Legzdins 6 D. Rosenfeld 7 Russell Wakeham 0000-0002-4304-0243 8
title Thermal Chemistry of Cp*W(NO)(H)(η3-allyl) Complexes
spellingShingle Thermal Chemistry of Cp*W(NO)(H)(η3-allyl) Complexes
Russell Wakeham
title_short Thermal Chemistry of Cp*W(NO)(H)(η3-allyl) Complexes
title_full Thermal Chemistry of Cp*W(NO)(H)(η3-allyl) Complexes
title_fullStr Thermal Chemistry of Cp*W(NO)(H)(η3-allyl) Complexes
title_full_unstemmed Thermal Chemistry of Cp*W(NO)(H)(η3-allyl) Complexes
title_sort Thermal Chemistry of Cp*W(NO)(H)(η3-allyl) Complexes
author_id_str_mv 28c45bbeeba294da7042950705b98e0a
author_id_fullname_str_mv 28c45bbeeba294da7042950705b98e0a_***_Russell Wakeham
author Russell Wakeham
author2 R. Baillie
R. Wakeham
G. Lefèvre
A. Béthegnies
B. Patrick
P. Legzdins
D. Rosenfeld
Russell Wakeham
format Journal article
container_title Organometallics
container_volume 34
container_issue 13
container_start_page 3428
publishDate 2015
institution Swansea University
issn 0276-7333
1520-6041
doi_str_mv 10.1021/acs.organomet.5b00426
publisher American Chemical Society (ACS)
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
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description The thermal properties of Cp*W(NO)(H)(η3-CH2CHCMe2) (1), Cp*W(NO)(H)(η3-CH2CHCHPh) (2), and Cp*W(NO)(H)(η3-CH2CHCHMe) (3) (Cp* = η5-C5Me5) have been investigated. Thermolyses of 1–3 in n-pentane lead to the loss of the original allyl ligand and the formation of the same mixture of isomeric products, namely, Cp*W(NO)(H)(η3-CH2CHCHEt) (4a) and Cp*W(NO)(H)(η3-MeCHCHCHMe) (4b) and their coordination isomers. Similarly, 1 reacts with cyclohexane and n-heptane to form Cp*W(NO)(H)(η3-C6H9) and isomers of Cp*W(NO)(H)(η3-C7H13), respectively. It is likely that complexes 1–3 first effect the selective, single-terminal C–H activation of the linear alkanes, but the first-formed products are thermally unstable and undergo two additional successive C–H activations to form the final allyl complexes. Consistent with this view is the fact that a bis(alkyl) intermediate complex can be trapped with N-methylmorpholine. Thus, the thermolysis of 1 in N-methylmorpholine affords a single organometallic complex, Cp*W(NO)(η2-CH2NC4H8O)(η1-CH2CH2CHMe2) (7). Complexes 2 and 3 react with N-methylmorpholine in an identical manner. Finally, 1 effects the multiple C–H activations of 1-chloropropane and 1-chlorobutane and forms the corresponding Cp*W(NO)(Cl)(η3-allyl) complexes. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.
published_date 2015-07-31T03:40:10Z
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score 11.036334

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