A computational study of the effects of ancillary ligands on copper( i )–ethylene interaction
A set of [Cu (I) L n (C 2 H 4 )] q ( q = −1, 0, or 1) complex modelling systems of experimental interest were studied by DFT calculations to analyze the Cu (I) –ethylene bonding using NBO and CDA analyses. All complexes are better viewed as donor–acceptor complexes between a d 10 Cu (I) center and e...
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| Veröffentlicht in: | New journal of chemistry 2015-01, Vol.39 (7), p.5410-5419 |
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| container_title | New journal of chemistry |
| container_volume | 39 |
| creator | Halbert, Stéphanie Gérard, Hélène |
| description | A set of [Cu
(I)
L
n
(C
2
H
4
)]
q
(
q
= −1, 0, or 1) complex modelling systems of experimental interest were studied by DFT calculations to analyze the Cu
(I)
–ethylene bonding using NBO and CDA analyses. All complexes are better viewed as donor–acceptor complexes between a d
10
Cu
(I)
center and ethylene. Back-donation depends significantly on the nature and number of ancillary ligands, and hence on the coordination sphere at copper. Back-donation is shown to vary more with the nature of the ligands than donation and to increase significantly with the number of ancillary ligands. However, even with strongly donating ligands such as alkyl (modelled by CH
3
), there is no tendency of forming a metallacyclopropane. This can lead to revisiting the mechanisms of alkylation of olefin catalyzed by copper complexes. |
| doi_str_mv | 10.1039/C5NJ00546A |
| format | Article |
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(I)
L
n
(C
2
H
4
)]
q
(
q
= −1, 0, or 1) complex modelling systems of experimental interest were studied by DFT calculations to analyze the Cu
(I)
–ethylene bonding using NBO and CDA analyses. All complexes are better viewed as donor–acceptor complexes between a d
10
Cu
(I)
center and ethylene. Back-donation depends significantly on the nature and number of ancillary ligands, and hence on the coordination sphere at copper. Back-donation is shown to vary more with the nature of the ligands than donation and to increase significantly with the number of ancillary ligands. However, even with strongly donating ligands such as alkyl (modelled by CH
3
), there is no tendency of forming a metallacyclopropane. This can lead to revisiting the mechanisms of alkylation of olefin catalyzed by copper complexes.</description><identifier>ISSN: 1144-0546</identifier><identifier>EISSN: 1369-9261</identifier><identifier>DOI: 10.1039/C5NJ00546A</identifier><language>eng</language><publisher>Royal Society of Chemistry [1987-....]</publisher><subject>Chemical Sciences</subject><ispartof>New journal of chemistry, 2015-01, Vol.39 (7), p.5410-5419</ispartof><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c301t-74c3170e369f4cc2b61c1911fa00398b60a600799282a59195e22f09838df37c3</citedby><cites>FETCH-LOGICAL-c301t-74c3170e369f4cc2b61c1911fa00398b60a600799282a59195e22f09838df37c3</cites><orcidid>0000-0002-8935-9591 ; 0000-0002-1961-9204</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,776,780,881,27903,27904</link.rule.ids><backlink>$$Uhttps://hal.sorbonne-universite.fr/hal-01176228$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Halbert, Stéphanie</creatorcontrib><creatorcontrib>Gérard, Hélène</creatorcontrib><title>A computational study of the effects of ancillary ligands on copper( i )–ethylene interaction</title><title>New journal of chemistry</title><description>A set of [Cu
(I)
L
n
(C
2
H
4
)]
q
(
q
= −1, 0, or 1) complex modelling systems of experimental interest were studied by DFT calculations to analyze the Cu
(I)
–ethylene bonding using NBO and CDA analyses. All complexes are better viewed as donor–acceptor complexes between a d
10
Cu
(I)
center and ethylene. Back-donation depends significantly on the nature and number of ancillary ligands, and hence on the coordination sphere at copper. Back-donation is shown to vary more with the nature of the ligands than donation and to increase significantly with the number of ancillary ligands. However, even with strongly donating ligands such as alkyl (modelled by CH
3
), there is no tendency of forming a metallacyclopropane. This can lead to revisiting the mechanisms of alkylation of olefin catalyzed by copper complexes.</description><subject>Chemical Sciences</subject><issn>1144-0546</issn><issn>1369-9261</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNpFUEFOwzAQtBBIlMKFF_hIkQJeO3HiYxQBBVVwgbPlujY1cpModpF64w_8kJfgUASn3Z2dGe0sQudAroAwcd0Ujw-EFDmvD9AEGBeZoBwOUw95no2LY3QSwhshACWHCZI11t2m30YVXdcqj0Pcrna4sziuDTbWGh3DOKpWO-_VsMPevap2lcA2SfveDBfY4dnXx6eJ6503rcGujWZQenQ8RUdW-WDOfusUvdzePDfzbPF0d9_Ui0wzAjErc82gJCZdbHOt6ZKDBgFgFUmxqiUnihNSCkErqgoBojCUWiIqVq0sKzWbotned6287Ae3SZfKTjk5rxdyxH4CU1q9Q-Je7rl66EIYjP0TAJHjG-X_G9k3qBNkOA</recordid><startdate>20150101</startdate><enddate>20150101</enddate><creator>Halbert, Stéphanie</creator><creator>Gérard, Hélène</creator><general>Royal Society of Chemistry [1987-....]</general><scope>AAYXX</scope><scope>CITATION</scope><scope>1XC</scope><scope>VOOES</scope><orcidid>https://orcid.org/0000-0002-8935-9591</orcidid><orcidid>https://orcid.org/0000-0002-1961-9204</orcidid></search><sort><creationdate>20150101</creationdate><title>A computational study of the effects of ancillary ligands on copper( i )–ethylene interaction</title><author>Halbert, Stéphanie ; Gérard, Hélène</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c301t-74c3170e369f4cc2b61c1911fa00398b60a600799282a59195e22f09838df37c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Chemical Sciences</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Halbert, Stéphanie</creatorcontrib><creatorcontrib>Gérard, Hélène</creatorcontrib><collection>CrossRef</collection><collection>Hyper Article en Ligne (HAL)</collection><collection>Hyper Article en Ligne (HAL) (Open Access)</collection><jtitle>New journal of chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Halbert, Stéphanie</au><au>Gérard, Hélène</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A computational study of the effects of ancillary ligands on copper( i )–ethylene interaction</atitle><jtitle>New journal of chemistry</jtitle><date>2015-01-01</date><risdate>2015</risdate><volume>39</volume><issue>7</issue><spage>5410</spage><epage>5419</epage><pages>5410-5419</pages><issn>1144-0546</issn><eissn>1369-9261</eissn><abstract>A set of [Cu
(I)
L
n
(C
2
H
4
)]
q
(
q
= −1, 0, or 1) complex modelling systems of experimental interest were studied by DFT calculations to analyze the Cu
(I)
–ethylene bonding using NBO and CDA analyses. All complexes are better viewed as donor–acceptor complexes between a d
10
Cu
(I)
center and ethylene. Back-donation depends significantly on the nature and number of ancillary ligands, and hence on the coordination sphere at copper. Back-donation is shown to vary more with the nature of the ligands than donation and to increase significantly with the number of ancillary ligands. However, even with strongly donating ligands such as alkyl (modelled by CH
3
), there is no tendency of forming a metallacyclopropane. This can lead to revisiting the mechanisms of alkylation of olefin catalyzed by copper complexes.</abstract><pub>Royal Society of Chemistry [1987-....]</pub><doi>10.1039/C5NJ00546A</doi><tpages>10</tpages><orcidid>https://orcid.org/0000-0002-8935-9591</orcidid><orcidid>https://orcid.org/0000-0002-1961-9204</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1144-0546 |
| ispartof | New journal of chemistry, 2015-01, Vol.39 (7), p.5410-5419 |
| issn | 1144-0546 1369-9261 |
| language | eng |
| recordid | cdi_hal_primary_oai_HAL_hal_01176228v1 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Chemical Sciences |
| title | A computational study of the effects of ancillary ligands on copper( i )–ethylene interaction |
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