Valence‐to‐Core X‐ray Emission Spectroscopy as a Probe of O−O Bond Activation in Cu 2 O 2 Complexes
Valence‐to‐Core (VtC) X‐ray emission spectroscopy (XES) was used to directly detect the presence of an O−O bond in a complex comprising the [Cu II 2 (μ‐η 2 :η 2 ‐O 2 )] 2+ core relative to its isomer with a cleaved O−O bond having a [Cu III 2 (μ‐O) 2 ] 2+ unit. The experimental studies are complemen...
Gespeichert in:
| Veröffentlicht in: | Angewandte Chemie 2019-07, Vol.131 (27), p.9212-9217 |
|---|---|
| Hauptverfasser: | , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 9217 |
|---|---|
| container_issue | 27 |
| container_start_page | 9212 |
| container_title | Angewandte Chemie |
| container_volume | 131 |
| creator | Cutsail, George E. Gagnon, Nicole L. Spaeth, Andrew D. Tolman, William B. DeBeer, Serena |
| description | Valence‐to‐Core (VtC) X‐ray emission spectroscopy (XES) was used to directly detect the presence of an O−O bond in a complex comprising the [Cu
II
2
(μ‐η
2
:η
2
‐O
2
)]
2+
core relative to its isomer with a cleaved O−O bond having a [Cu
III
2
(μ‐O)
2
]
2+
unit. The experimental studies are complemented by DFT calculations, which show that the unique VtC XES feature of the [Cu
II
2
(μ‐η
2
:η
2
‐O
2
)]
2+
core corresponds to the copper stabilized in‐plane 2p π peroxo molecular orbital. These calculations illustrate the sensitivity of VtC XES for probing the extent of O−O bond activation in μ‐η
2
:η
2
‐O
2
species and highlight the potential of this method for time‐resolved studies of reaction mechanisms. |
| doi_str_mv | 10.1002/ange.201903749 |
| format | Article |
| fullrecord | <record><control><sourceid>crossref</sourceid><recordid>TN_cdi_crossref_primary_10_1002_ange_201903749</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>10_1002_ange_201903749</sourcerecordid><originalsourceid>FETCH-LOGICAL-c849-b0acf1e9e4fb09f884cd13b151bf9f761067eaef1878ecf0b68fda7f674926733</originalsourceid><addsrcrecordid>eNo9kM1OwzAQhC0EEqVw5ewXSFk7bmwfS1R-pEpBokLcIsdZo0AaR3ZA9MaRI-IR-ySkAnHY3bnMauYj5JzBjAHwC9M94YwD05BKoQ_IhM05S1I5l4dkAiBEorjQx-QkxmcAyLjUE_LyYFrsLO4-vgY_rtwHpI-jCGZLl5smxsZ39L5HOwQfre-31ERq6F3wFVLvaLH7_C7ope9qurBD82aGvaHpaP5KOS3Gyf2mb_Ed4yk5cqaNePZ3p2R9tVznN8mquL7NF6vEKqGTCox1DDUKV4F2Sglbs7Ric1Y57WTGIJNo0DElFVoHVaZcbaTLxtI8k2k6JbPft3ZMHAO6sg_NxoRtyaDckyr3pMp_UukP8BFgCA</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Valence‐to‐Core X‐ray Emission Spectroscopy as a Probe of O−O Bond Activation in Cu 2 O 2 Complexes</title><source>Wiley Online Library Journals Frontfile Complete</source><creator>Cutsail, George E. ; Gagnon, Nicole L. ; Spaeth, Andrew D. ; Tolman, William B. ; DeBeer, Serena</creator><creatorcontrib>Cutsail, George E. ; Gagnon, Nicole L. ; Spaeth, Andrew D. ; Tolman, William B. ; DeBeer, Serena</creatorcontrib><description>Valence‐to‐Core (VtC) X‐ray emission spectroscopy (XES) was used to directly detect the presence of an O−O bond in a complex comprising the [Cu
II
2
(μ‐η
2
:η
2
‐O
2
)]
2+
core relative to its isomer with a cleaved O−O bond having a [Cu
III
2
(μ‐O)
2
]
2+
unit. The experimental studies are complemented by DFT calculations, which show that the unique VtC XES feature of the [Cu
II
2
(μ‐η
2
:η
2
‐O
2
)]
2+
core corresponds to the copper stabilized in‐plane 2p π peroxo molecular orbital. These calculations illustrate the sensitivity of VtC XES for probing the extent of O−O bond activation in μ‐η
2
:η
2
‐O
2
species and highlight the potential of this method for time‐resolved studies of reaction mechanisms.</description><identifier>ISSN: 0044-8249</identifier><identifier>EISSN: 1521-3757</identifier><identifier>DOI: 10.1002/ange.201903749</identifier><language>eng</language><ispartof>Angewandte Chemie, 2019-07, Vol.131 (27), p.9212-9217</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c849-b0acf1e9e4fb09f884cd13b151bf9f761067eaef1878ecf0b68fda7f674926733</citedby><cites>FETCH-LOGICAL-c849-b0acf1e9e4fb09f884cd13b151bf9f761067eaef1878ecf0b68fda7f674926733</cites><orcidid>0000-0002-2243-6409 ; 0000-0002-4265-6150 ; 0000-0002-7378-9474 ; 0000-0002-5196-3400 ; 0000-0002-3091-1548</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,778,782,27907,27908</link.rule.ids></links><search><creatorcontrib>Cutsail, George E.</creatorcontrib><creatorcontrib>Gagnon, Nicole L.</creatorcontrib><creatorcontrib>Spaeth, Andrew D.</creatorcontrib><creatorcontrib>Tolman, William B.</creatorcontrib><creatorcontrib>DeBeer, Serena</creatorcontrib><title>Valence‐to‐Core X‐ray Emission Spectroscopy as a Probe of O−O Bond Activation in Cu 2 O 2 Complexes</title><title>Angewandte Chemie</title><description>Valence‐to‐Core (VtC) X‐ray emission spectroscopy (XES) was used to directly detect the presence of an O−O bond in a complex comprising the [Cu
II
2
(μ‐η
2
:η
2
‐O
2
)]
2+
core relative to its isomer with a cleaved O−O bond having a [Cu
III
2
(μ‐O)
2
]
2+
unit. The experimental studies are complemented by DFT calculations, which show that the unique VtC XES feature of the [Cu
II
2
(μ‐η
2
:η
2
‐O
2
)]
2+
core corresponds to the copper stabilized in‐plane 2p π peroxo molecular orbital. These calculations illustrate the sensitivity of VtC XES for probing the extent of O−O bond activation in μ‐η
2
:η
2
‐O
2
species and highlight the potential of this method for time‐resolved studies of reaction mechanisms.</description><issn>0044-8249</issn><issn>1521-3757</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNo9kM1OwzAQhC0EEqVw5ewXSFk7bmwfS1R-pEpBokLcIsdZo0AaR3ZA9MaRI-IR-ySkAnHY3bnMauYj5JzBjAHwC9M94YwD05BKoQ_IhM05S1I5l4dkAiBEorjQx-QkxmcAyLjUE_LyYFrsLO4-vgY_rtwHpI-jCGZLl5smxsZ39L5HOwQfre-31ERq6F3wFVLvaLH7_C7ope9qurBD82aGvaHpaP5KOS3Gyf2mb_Ed4yk5cqaNePZ3p2R9tVznN8mquL7NF6vEKqGTCox1DDUKV4F2Sglbs7Ric1Y57WTGIJNo0DElFVoHVaZcbaTLxtI8k2k6JbPft3ZMHAO6sg_NxoRtyaDckyr3pMp_UukP8BFgCA</recordid><startdate>201907</startdate><enddate>201907</enddate><creator>Cutsail, George E.</creator><creator>Gagnon, Nicole L.</creator><creator>Spaeth, Andrew D.</creator><creator>Tolman, William B.</creator><creator>DeBeer, Serena</creator><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0002-2243-6409</orcidid><orcidid>https://orcid.org/0000-0002-4265-6150</orcidid><orcidid>https://orcid.org/0000-0002-7378-9474</orcidid><orcidid>https://orcid.org/0000-0002-5196-3400</orcidid><orcidid>https://orcid.org/0000-0002-3091-1548</orcidid></search><sort><creationdate>201907</creationdate><title>Valence‐to‐Core X‐ray Emission Spectroscopy as a Probe of O−O Bond Activation in Cu 2 O 2 Complexes</title><author>Cutsail, George E. ; Gagnon, Nicole L. ; Spaeth, Andrew D. ; Tolman, William B. ; DeBeer, Serena</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c849-b0acf1e9e4fb09f884cd13b151bf9f761067eaef1878ecf0b68fda7f674926733</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Cutsail, George E.</creatorcontrib><creatorcontrib>Gagnon, Nicole L.</creatorcontrib><creatorcontrib>Spaeth, Andrew D.</creatorcontrib><creatorcontrib>Tolman, William B.</creatorcontrib><creatorcontrib>DeBeer, Serena</creatorcontrib><collection>CrossRef</collection><jtitle>Angewandte Chemie</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Cutsail, George E.</au><au>Gagnon, Nicole L.</au><au>Spaeth, Andrew D.</au><au>Tolman, William B.</au><au>DeBeer, Serena</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Valence‐to‐Core X‐ray Emission Spectroscopy as a Probe of O−O Bond Activation in Cu 2 O 2 Complexes</atitle><jtitle>Angewandte Chemie</jtitle><date>2019-07</date><risdate>2019</risdate><volume>131</volume><issue>27</issue><spage>9212</spage><epage>9217</epage><pages>9212-9217</pages><issn>0044-8249</issn><eissn>1521-3757</eissn><abstract>Valence‐to‐Core (VtC) X‐ray emission spectroscopy (XES) was used to directly detect the presence of an O−O bond in a complex comprising the [Cu
II
2
(μ‐η
2
:η
2
‐O
2
)]
2+
core relative to its isomer with a cleaved O−O bond having a [Cu
III
2
(μ‐O)
2
]
2+
unit. The experimental studies are complemented by DFT calculations, which show that the unique VtC XES feature of the [Cu
II
2
(μ‐η
2
:η
2
‐O
2
)]
2+
core corresponds to the copper stabilized in‐plane 2p π peroxo molecular orbital. These calculations illustrate the sensitivity of VtC XES for probing the extent of O−O bond activation in μ‐η
2
:η
2
‐O
2
species and highlight the potential of this method for time‐resolved studies of reaction mechanisms.</abstract><doi>10.1002/ange.201903749</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0002-2243-6409</orcidid><orcidid>https://orcid.org/0000-0002-4265-6150</orcidid><orcidid>https://orcid.org/0000-0002-7378-9474</orcidid><orcidid>https://orcid.org/0000-0002-5196-3400</orcidid><orcidid>https://orcid.org/0000-0002-3091-1548</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0044-8249 |
| ispartof | Angewandte Chemie, 2019-07, Vol.131 (27), p.9212-9217 |
| issn | 0044-8249 1521-3757 |
| language | eng |
| recordid | cdi_crossref_primary_10_1002_ange_201903749 |
| source | Wiley Online Library Journals Frontfile Complete |
| title | Valence‐to‐Core X‐ray Emission Spectroscopy as a Probe of O−O Bond Activation in Cu 2 O 2 Complexes |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-16T09%3A09%3A20IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-crossref&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Valence%E2%80%90to%E2%80%90Core%20X%E2%80%90ray%20Emission%20Spectroscopy%20as%20a%20Probe%20of%20O%E2%88%92O%20Bond%20Activation%20in%20Cu%202%20O%202%20Complexes&rft.jtitle=Angewandte%20Chemie&rft.au=Cutsail,%20George%20E.&rft.date=2019-07&rft.volume=131&rft.issue=27&rft.spage=9212&rft.epage=9217&rft.pages=9212-9217&rft.issn=0044-8249&rft.eissn=1521-3757&rft_id=info:doi/10.1002/ange.201903749&rft_dat=%3Ccrossref%3E10_1002_ange_201903749%3C/crossref%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true |