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Thermal Chemistry of Cp*W(NO)(CH2CMe3)(H)(L) Complexes (L = Lewis Base)

Diana Fabulyak, Rex C. Handford, Aaron S. Holmes, Taleah M. Levesque, Russell Wakeham Orcid Logo, Brian O. Patrick, Peter Legzdins, Devon C. Rosenfeld

Inorganic Chemistry, Volume: 56, Issue: 1, Pages: 573 - 582

Swansea University Author: Russell Wakeham Orcid Logo

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DOI (Published version): 10.1021/acs.inorgchem.6b02431

Abstract

The complexes trans-Cp*W(NO)(CH2CMe3)(H)(L) (Cp* = η5-C5Me5) result from the treatment of Cp*W(NO)(CH2CMe3)2 in n-pentane with H2 (∼1 atm) in the presence of a Lewis base, L. The designation of a particular geometrical isomer as cis or trans indicates the relative positions of the alkyl and hydrido...

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Published in: Inorganic Chemistry
ISSN: 0020-1669 1520-510X
Published: American Chemical Society (ACS) 2017
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URI: https://cronfa.swan.ac.uk/Record/cronfa32705
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fullrecord <?xml version="1.0"?><rfc1807><datestamp>2017-07-07T15:42:56.5187995</datestamp><bib-version>v2</bib-version><id>32705</id><entry>2017-03-27</entry><title>Thermal Chemistry of Cp*W(NO)(CH2CMe3)(H)(L) Complexes (L = Lewis Base)</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 complexes trans-Cp*W(NO)(CH2CMe3)(H)(L) (Cp* = &#x3B7;5-C5Me5) result from the treatment of Cp*W(NO)(CH2CMe3)2 in n-pentane with H2 (&#x223C;1 atm) in the presence of a Lewis base, L. The designation of a particular geometrical isomer as cis or trans indicates the relative positions of the alkyl and hydrido ligands in the base of a four-legged piano-stool molecular structure. The thermal behavior of these complexes is markedly dependent on the nature of L. Some of them can be isolated at ambient temperatures [e.g., L = P(OMe)3, P(OPh)3, or P(OCH2)3CMe]. Others undergo reductive elimination of CMe4 via trans to cis isomerization to generate the 16e reactive intermediates Cp*W(NO)(L). These intermediates can intramolecularly activate a C&#x2013;H bond of L to form 18e cis complexes that may convert to the thermodynamically more stable trans isomers [e.g., Cp*W(NO)(PPh3) initially forms cis-Cp*W(NO)(H)(&#x3BA;2-PPh2C6H4) that upon being warmed in n-pentane at 80 &#xB0;C isomerizes to trans-Cp*W(NO)(H)(&#x3BA;2-PPh2C6H4)]. Alternatively, the Cp*W(NO)(L) intermediates can effect the intermolecular activation of a substrate R-H to form trans-Cp*W(NO)(R)(H)(L) complexes [e.g., L = P(OMe)3 or P(OCH2)3CMe; R-H = C6H6 or Me4Si] probably via their cis isomers. These latter activations are also accompanied by the formation of some Cp*W(NO)(L)2 disproportionation products. An added complication in the L = P(OMe)3 system is that thermolysis of trans-Cp*W(NO)(CH2CMe3)(H)(P(OMe)3) results in it undergoing an Arbuzov-like rearrangement and being converted mainly into [Cp*W(NO)(Me)(PO(OMe)2)]2, which exists as a mixture of two isomers. All new complexes have been characterized by conventional and spectroscopic 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>Inorganic Chemistry</journal><volume>56</volume><journalNumber>1</journalNumber><paginationStart>573</paginationStart><paginationEnd>582</paginationEnd><publisher>American Chemical Society (ACS)</publisher><issnPrint>0020-1669</issnPrint><issnElectronic>1520-510X</issnElectronic><keywords/><publishedDay>3</publishedDay><publishedMonth>1</publishedMonth><publishedYear>2017</publishedYear><publishedDate>2017-01-03</publishedDate><doi>10.1021/acs.inorgchem.6b02431</doi><url/><notes/><college>COLLEGE NANME</college><department>Engineering</department><CollegeCode>COLLEGE CODE</CollegeCode><DepartmentCode>EEN</DepartmentCode><institution>Swansea University</institution><apcterm/><lastEdited>2017-07-07T15:42:56.5187995</lastEdited><Created>2017-03-27T11:03:19.7704184</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>Diana</firstname><surname>Fabulyak</surname><order>1</order></author><author><firstname>Rex C.</firstname><surname>Handford</surname><order>2</order></author><author><firstname>Aaron S.</firstname><surname>Holmes</surname><order>3</order></author><author><firstname>Taleah M.</firstname><surname>Levesque</surname><order>4</order></author><author><firstname>Russell</firstname><surname>Wakeham</surname><orcid>0000-0002-4304-0243</orcid><order>5</order></author><author><firstname>Brian O.</firstname><surname>Patrick</surname><order>6</order></author><author><firstname>Peter</firstname><surname>Legzdins</surname><order>7</order></author><author><firstname>Devon C.</firstname><surname>Rosenfeld</surname><order>8</order></author></authors><documents/><OutputDurs/></rfc1807>
spelling 2017-07-07T15:42:56.5187995 v2 32705 2017-03-27 Thermal Chemistry of Cp*W(NO)(CH2CMe3)(H)(L) Complexes (L = Lewis Base) 28c45bbeeba294da7042950705b98e0a 0000-0002-4304-0243 Russell Wakeham Russell Wakeham true false 2017-03-27 EEN The complexes trans-Cp*W(NO)(CH2CMe3)(H)(L) (Cp* = η5-C5Me5) result from the treatment of Cp*W(NO)(CH2CMe3)2 in n-pentane with H2 (∼1 atm) in the presence of a Lewis base, L. The designation of a particular geometrical isomer as cis or trans indicates the relative positions of the alkyl and hydrido ligands in the base of a four-legged piano-stool molecular structure. The thermal behavior of these complexes is markedly dependent on the nature of L. Some of them can be isolated at ambient temperatures [e.g., L = P(OMe)3, P(OPh)3, or P(OCH2)3CMe]. Others undergo reductive elimination of CMe4 via trans to cis isomerization to generate the 16e reactive intermediates Cp*W(NO)(L). These intermediates can intramolecularly activate a C–H bond of L to form 18e cis complexes that may convert to the thermodynamically more stable trans isomers [e.g., Cp*W(NO)(PPh3) initially forms cis-Cp*W(NO)(H)(κ2-PPh2C6H4) that upon being warmed in n-pentane at 80 °C isomerizes to trans-Cp*W(NO)(H)(κ2-PPh2C6H4)]. Alternatively, the Cp*W(NO)(L) intermediates can effect the intermolecular activation of a substrate R-H to form trans-Cp*W(NO)(R)(H)(L) complexes [e.g., L = P(OMe)3 or P(OCH2)3CMe; R-H = C6H6 or Me4Si] probably via their cis isomers. These latter activations are also accompanied by the formation of some Cp*W(NO)(L)2 disproportionation products. An added complication in the L = P(OMe)3 system is that thermolysis of trans-Cp*W(NO)(CH2CMe3)(H)(P(OMe)3) results in it undergoing an Arbuzov-like rearrangement and being converted mainly into [Cp*W(NO)(Me)(PO(OMe)2)]2, which exists as a mixture of two isomers. All new complexes have been characterized by conventional and spectroscopic methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses. Journal Article Inorganic Chemistry 56 1 573 582 American Chemical Society (ACS) 0020-1669 1520-510X 3 1 2017 2017-01-03 10.1021/acs.inorgchem.6b02431 COLLEGE NANME Engineering COLLEGE CODE EEN Swansea University 2017-07-07T15:42:56.5187995 2017-03-27T11:03:19.7704184 Faculty of Science and Engineering School of Engineering and Applied Sciences - Uncategorised Diana Fabulyak 1 Rex C. Handford 2 Aaron S. Holmes 3 Taleah M. Levesque 4 Russell Wakeham 0000-0002-4304-0243 5 Brian O. Patrick 6 Peter Legzdins 7 Devon C. Rosenfeld 8
title Thermal Chemistry of Cp*W(NO)(CH2CMe3)(H)(L) Complexes (L = Lewis Base)
spellingShingle Thermal Chemistry of Cp*W(NO)(CH2CMe3)(H)(L) Complexes (L = Lewis Base)
Russell Wakeham
title_short Thermal Chemistry of Cp*W(NO)(CH2CMe3)(H)(L) Complexes (L = Lewis Base)
title_full Thermal Chemistry of Cp*W(NO)(CH2CMe3)(H)(L) Complexes (L = Lewis Base)
title_fullStr Thermal Chemistry of Cp*W(NO)(CH2CMe3)(H)(L) Complexes (L = Lewis Base)
title_full_unstemmed Thermal Chemistry of Cp*W(NO)(CH2CMe3)(H)(L) Complexes (L = Lewis Base)
title_sort Thermal Chemistry of Cp*W(NO)(CH2CMe3)(H)(L) Complexes (L = Lewis Base)
author_id_str_mv 28c45bbeeba294da7042950705b98e0a
author_id_fullname_str_mv 28c45bbeeba294da7042950705b98e0a_***_Russell Wakeham
author Russell Wakeham
author2 Diana Fabulyak
Rex C. Handford
Aaron S. Holmes
Taleah M. Levesque
Russell Wakeham
Brian O. Patrick
Peter Legzdins
Devon C. Rosenfeld
format Journal article
container_title Inorganic Chemistry
container_volume 56
container_issue 1
container_start_page 573
publishDate 2017
institution Swansea University
issn 0020-1669
1520-510X
doi_str_mv 10.1021/acs.inorgchem.6b02431
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
active_str 0
description The complexes trans-Cp*W(NO)(CH2CMe3)(H)(L) (Cp* = η5-C5Me5) result from the treatment of Cp*W(NO)(CH2CMe3)2 in n-pentane with H2 (∼1 atm) in the presence of a Lewis base, L. The designation of a particular geometrical isomer as cis or trans indicates the relative positions of the alkyl and hydrido ligands in the base of a four-legged piano-stool molecular structure. The thermal behavior of these complexes is markedly dependent on the nature of L. Some of them can be isolated at ambient temperatures [e.g., L = P(OMe)3, P(OPh)3, or P(OCH2)3CMe]. Others undergo reductive elimination of CMe4 via trans to cis isomerization to generate the 16e reactive intermediates Cp*W(NO)(L). These intermediates can intramolecularly activate a C–H bond of L to form 18e cis complexes that may convert to the thermodynamically more stable trans isomers [e.g., Cp*W(NO)(PPh3) initially forms cis-Cp*W(NO)(H)(κ2-PPh2C6H4) that upon being warmed in n-pentane at 80 °C isomerizes to trans-Cp*W(NO)(H)(κ2-PPh2C6H4)]. Alternatively, the Cp*W(NO)(L) intermediates can effect the intermolecular activation of a substrate R-H to form trans-Cp*W(NO)(R)(H)(L) complexes [e.g., L = P(OMe)3 or P(OCH2)3CMe; R-H = C6H6 or Me4Si] probably via their cis isomers. These latter activations are also accompanied by the formation of some Cp*W(NO)(L)2 disproportionation products. An added complication in the L = P(OMe)3 system is that thermolysis of trans-Cp*W(NO)(CH2CMe3)(H)(P(OMe)3) results in it undergoing an Arbuzov-like rearrangement and being converted mainly into [Cp*W(NO)(Me)(PO(OMe)2)]2, which exists as a mixture of two isomers. All new complexes have been characterized by conventional and spectroscopic methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.
published_date 2017-01-03T03:40:10Z
_version_ 1763751819156127744
score 11.012678

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