Spectroscopic Manifestations and Implications for Catalysis of Quasi-d 10 Configurations in Formal Gold(III) Complexes
Several gold +I and +III complexes are investigated computationally and spectroscopically, focusing on the d-configuration and physical oxidation state of the metal center. Density functional theory calculations reveal the non-negligible electron-sharing covalent character of the metal-to-ligand σ-b...
Gespeichert in:
Veröffentlicht in: | Angewandte Chemie International Edition 2023-01, Vol.62 (3), p.e202215523 |
---|---|
Hauptverfasser: | , , , , , |
Format: | Artikel |
Sprache: | eng |
Online-Zugang: | Volltext |
Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
container_end_page | |
---|---|
container_issue | 3 |
container_start_page | e202215523 |
container_title | Angewandte Chemie International Edition |
container_volume | 62 |
creator | Trifonova, Evgeniya A Leach, Isaac F de Haas, Winfried B Havenith, Remco W A Tromp, Moniek Klein, Johannes E M N |
description | Several gold +I and +III complexes are investigated computationally and spectroscopically, focusing on the d-configuration and physical oxidation state of the metal center. Density functional theory calculations reveal the non-negligible electron-sharing covalent character of the metal-to-ligand σ-bonding framework. The bonding of gold(III) is shown to be isoelectronic to the formal Cu
complex [Cu(CF
)
]
, in which the metal center tries to populate its formally unoccupied 3d
orbital via σ-bonding, leading to a reduced d
Cu
description. However, Au L
-edge X-ray absorption spectroscopy reveals excitation into the d-orbital of the Au
species is still possible, showing that a genuine d
configuration is not achieved. We also find an increased electron-sharing nature of the σ-bonds in the Au
species, relative to their Ag
and Cu
analogues, due to the low-lying 6s orbital. We propose that gold +I and +III complexes form similar bonds with substrates, owing primarily to participation of the 5d
or 6s orbital, respectively, in bonding, indicating why Au
and Au
complexes often have similar reactivity. |
doi_str_mv | 10.1002/anie.202215523 |
format | Article |
fullrecord | <record><control><sourceid>pubmed_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1002_anie_202215523</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>36508713</sourcerecordid><originalsourceid>FETCH-LOGICAL-c1073-2eec2da7ca21073e84cccc5766d1f3eb7fe25e17b47f4309413e4f2c309c4bfc3</originalsourceid><addsrcrecordid>eNo9kN1LwzAUxYMobk5ffZQ86kNrvtrURyluFiYi6nNJ0xuJtE1JOnH_vRmbuy_3g3MO3B9C15SklBB2rwYLKSOM0Sxj_ATNacZowqXkp3EWnCeyyOgMXYTwHfVFQfJzNON5RgpJ-Rz9vI-gJ--CdqPV-CXmGQiTmqwbAlZDi6t-7Kw-HIzzuFST6rbBBuwMftuoYJMWU4JLNxj7tfEHqR3w0vledXjluva2qqq7KIlh8AvhEp0Z1QW4OvQF-lw-fZTPyfp1VZWP60RTInnCADRrldSK7XYohI6VyTxvqeHQSAMsAyobIY3g5EFQDsIwHUctGqP5AqX7XB1fDB5MPXrbK7-tKal3AOsdwPoIMBpu9oZx0_TQHuX_xPgfu5NtnQ</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Spectroscopic Manifestations and Implications for Catalysis of Quasi-d 10 Configurations in Formal Gold(III) Complexes</title><source>Access via Wiley Online Library</source><creator>Trifonova, Evgeniya A ; Leach, Isaac F ; de Haas, Winfried B ; Havenith, Remco W A ; Tromp, Moniek ; Klein, Johannes E M N</creator><creatorcontrib>Trifonova, Evgeniya A ; Leach, Isaac F ; de Haas, Winfried B ; Havenith, Remco W A ; Tromp, Moniek ; Klein, Johannes E M N</creatorcontrib><description>Several gold +I and +III complexes are investigated computationally and spectroscopically, focusing on the d-configuration and physical oxidation state of the metal center. Density functional theory calculations reveal the non-negligible electron-sharing covalent character of the metal-to-ligand σ-bonding framework. The bonding of gold(III) is shown to be isoelectronic to the formal Cu
complex [Cu(CF
)
]
, in which the metal center tries to populate its formally unoccupied 3d
orbital via σ-bonding, leading to a reduced d
Cu
description. However, Au L
-edge X-ray absorption spectroscopy reveals excitation into the d-orbital of the Au
species is still possible, showing that a genuine d
configuration is not achieved. We also find an increased electron-sharing nature of the σ-bonds in the Au
species, relative to their Ag
and Cu
analogues, due to the low-lying 6s orbital. We propose that gold +I and +III complexes form similar bonds with substrates, owing primarily to participation of the 5d
or 6s orbital, respectively, in bonding, indicating why Au
and Au
complexes often have similar reactivity.</description><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202215523</identifier><identifier>PMID: 36508713</identifier><language>eng</language><publisher>Germany</publisher><ispartof>Angewandte Chemie International Edition, 2023-01, Vol.62 (3), p.e202215523</ispartof><rights>2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c1073-2eec2da7ca21073e84cccc5766d1f3eb7fe25e17b47f4309413e4f2c309c4bfc3</citedby><cites>FETCH-LOGICAL-c1073-2eec2da7ca21073e84cccc5766d1f3eb7fe25e17b47f4309413e4f2c309c4bfc3</cites><orcidid>0000-0002-7653-1639 ; 0000-0003-0038-6030 ; 0000-0003-2973-6241 ; 0000-0001-7377-6561 ; 0000-0002-1538-7856 ; 0000-0002-1290-597X</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/36508713$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Trifonova, Evgeniya A</creatorcontrib><creatorcontrib>Leach, Isaac F</creatorcontrib><creatorcontrib>de Haas, Winfried B</creatorcontrib><creatorcontrib>Havenith, Remco W A</creatorcontrib><creatorcontrib>Tromp, Moniek</creatorcontrib><creatorcontrib>Klein, Johannes E M N</creatorcontrib><title>Spectroscopic Manifestations and Implications for Catalysis of Quasi-d 10 Configurations in Formal Gold(III) Complexes</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>Several gold +I and +III complexes are investigated computationally and spectroscopically, focusing on the d-configuration and physical oxidation state of the metal center. Density functional theory calculations reveal the non-negligible electron-sharing covalent character of the metal-to-ligand σ-bonding framework. The bonding of gold(III) is shown to be isoelectronic to the formal Cu
complex [Cu(CF
)
]
, in which the metal center tries to populate its formally unoccupied 3d
orbital via σ-bonding, leading to a reduced d
Cu
description. However, Au L
-edge X-ray absorption spectroscopy reveals excitation into the d-orbital of the Au
species is still possible, showing that a genuine d
configuration is not achieved. We also find an increased electron-sharing nature of the σ-bonds in the Au
species, relative to their Ag
and Cu
analogues, due to the low-lying 6s orbital. We propose that gold +I and +III complexes form similar bonds with substrates, owing primarily to participation of the 5d
or 6s orbital, respectively, in bonding, indicating why Au
and Au
complexes often have similar reactivity.</description><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNo9kN1LwzAUxYMobk5ffZQ86kNrvtrURyluFiYi6nNJ0xuJtE1JOnH_vRmbuy_3g3MO3B9C15SklBB2rwYLKSOM0Sxj_ATNacZowqXkp3EWnCeyyOgMXYTwHfVFQfJzNON5RgpJ-Rz9vI-gJ--CdqPV-CXmGQiTmqwbAlZDi6t-7Kw-HIzzuFST6rbBBuwMftuoYJMWU4JLNxj7tfEHqR3w0vledXjluva2qqq7KIlh8AvhEp0Z1QW4OvQF-lw-fZTPyfp1VZWP60RTInnCADRrldSK7XYohI6VyTxvqeHQSAMsAyobIY3g5EFQDsIwHUctGqP5AqX7XB1fDB5MPXrbK7-tKal3AOsdwPoIMBpu9oZx0_TQHuX_xPgfu5NtnQ</recordid><startdate>20230116</startdate><enddate>20230116</enddate><creator>Trifonova, Evgeniya A</creator><creator>Leach, Isaac F</creator><creator>de Haas, Winfried B</creator><creator>Havenith, Remco W A</creator><creator>Tromp, Moniek</creator><creator>Klein, Johannes E M N</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0002-7653-1639</orcidid><orcidid>https://orcid.org/0000-0003-0038-6030</orcidid><orcidid>https://orcid.org/0000-0003-2973-6241</orcidid><orcidid>https://orcid.org/0000-0001-7377-6561</orcidid><orcidid>https://orcid.org/0000-0002-1538-7856</orcidid><orcidid>https://orcid.org/0000-0002-1290-597X</orcidid></search><sort><creationdate>20230116</creationdate><title>Spectroscopic Manifestations and Implications for Catalysis of Quasi-d 10 Configurations in Formal Gold(III) Complexes</title><author>Trifonova, Evgeniya A ; Leach, Isaac F ; de Haas, Winfried B ; Havenith, Remco W A ; Tromp, Moniek ; Klein, Johannes E M N</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c1073-2eec2da7ca21073e84cccc5766d1f3eb7fe25e17b47f4309413e4f2c309c4bfc3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Trifonova, Evgeniya A</creatorcontrib><creatorcontrib>Leach, Isaac F</creatorcontrib><creatorcontrib>de Haas, Winfried B</creatorcontrib><creatorcontrib>Havenith, Remco W A</creatorcontrib><creatorcontrib>Tromp, Moniek</creatorcontrib><creatorcontrib>Klein, Johannes E M N</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Trifonova, Evgeniya A</au><au>Leach, Isaac F</au><au>de Haas, Winfried B</au><au>Havenith, Remco W A</au><au>Tromp, Moniek</au><au>Klein, Johannes E M N</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Spectroscopic Manifestations and Implications for Catalysis of Quasi-d 10 Configurations in Formal Gold(III) Complexes</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2023-01-16</date><risdate>2023</risdate><volume>62</volume><issue>3</issue><spage>e202215523</spage><pages>e202215523-</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>Several gold +I and +III complexes are investigated computationally and spectroscopically, focusing on the d-configuration and physical oxidation state of the metal center. Density functional theory calculations reveal the non-negligible electron-sharing covalent character of the metal-to-ligand σ-bonding framework. The bonding of gold(III) is shown to be isoelectronic to the formal Cu
complex [Cu(CF
)
]
, in which the metal center tries to populate its formally unoccupied 3d
orbital via σ-bonding, leading to a reduced d
Cu
description. However, Au L
-edge X-ray absorption spectroscopy reveals excitation into the d-orbital of the Au
species is still possible, showing that a genuine d
configuration is not achieved. We also find an increased electron-sharing nature of the σ-bonds in the Au
species, relative to their Ag
and Cu
analogues, due to the low-lying 6s orbital. We propose that gold +I and +III complexes form similar bonds with substrates, owing primarily to participation of the 5d
or 6s orbital, respectively, in bonding, indicating why Au
and Au
complexes often have similar reactivity.</abstract><cop>Germany</cop><pmid>36508713</pmid><doi>10.1002/anie.202215523</doi><orcidid>https://orcid.org/0000-0002-7653-1639</orcidid><orcidid>https://orcid.org/0000-0003-0038-6030</orcidid><orcidid>https://orcid.org/0000-0003-2973-6241</orcidid><orcidid>https://orcid.org/0000-0001-7377-6561</orcidid><orcidid>https://orcid.org/0000-0002-1538-7856</orcidid><orcidid>https://orcid.org/0000-0002-1290-597X</orcidid></addata></record> |
fulltext | fulltext |
identifier | ISSN: 1433-7851 |
ispartof | Angewandte Chemie International Edition, 2023-01, Vol.62 (3), p.e202215523 |
issn | 1433-7851 1521-3773 |
language | eng |
recordid | cdi_crossref_primary_10_1002_anie_202215523 |
source | Access via Wiley Online Library |
title | Spectroscopic Manifestations and Implications for Catalysis of Quasi-d 10 Configurations in Formal Gold(III) Complexes |
url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-24T21%3A10%3A23IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-pubmed_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Spectroscopic%20Manifestations%20and%20Implications%20for%20Catalysis%20of%20Quasi-d%2010%20Configurations%20in%20Formal%20Gold(III)%20Complexes&rft.jtitle=Angewandte%20Chemie%20International%20Edition&rft.au=Trifonova,%20Evgeniya%20A&rft.date=2023-01-16&rft.volume=62&rft.issue=3&rft.spage=e202215523&rft.pages=e202215523-&rft.issn=1433-7851&rft.eissn=1521-3773&rft_id=info:doi/10.1002/anie.202215523&rft_dat=%3Cpubmed_cross%3E36508713%3C/pubmed_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/36508713&rfr_iscdi=true |