Electron localization in a mixed-valence diniobium benzene complex
Reaction of the neutral diniobium benzene complex {[Nb(BDI)N Bu] (μ-C H )} (BDI = , '-diisopropylbenzene-β-diketiminate) with Ag[B(C F ) ] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N Bu] (μ-C H )}{B(C F ) }. Investigation of the solid state a...
Gespeichert in:
| Veröffentlicht in: | Chemical science (Cambridge) 2015-02, Vol.6 (2), p.993-1003 |
|---|---|
| Hauptverfasser: | , , , , , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 1003 |
|---|---|
| container_issue | 2 |
| container_start_page | 993 |
| container_title | Chemical science (Cambridge) |
| container_volume | 6 |
| creator | Gianetti, Thomas L Nocton, Grégory Minasian, Stefan G Kaltsoyannis, Nikolas Kilcoyne, A L David Kozimor, Stosh A Shuh, David K Tyliszczak, Tolek Bergman, Robert G Arnold, John |
| description | Reaction of the neutral diniobium benzene complex {[Nb(BDI)N
Bu]
(μ-C
H
)} (BDI =
,
'-diisopropylbenzene-β-diketiminate) with Ag[B(C
F
)
] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N
Bu]
(μ-C
H
)}{B(C
F
)
}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L
-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment of a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the δ-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex. |
| doi_str_mv | 10.1039/c4sc02705a |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_5811154</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2016534352</sourcerecordid><originalsourceid>FETCH-LOGICAL-c538t-4ad44f7d1a90696ce880fbce7e1aa3e558122dd798857f0c9da14d4d11e79c593</originalsourceid><addsrcrecordid>eNqFkU1vEzEQhlcIRKvSCz8ArTgB0oLHH2v7gpRGhSJF4gCcLceeJUZeO6w3UemvxyElAi744q9Hz4zmbZqnQF4DYfqN48URKomwD5pzSjh0vWD64elMyVlzWco3UhdjIKh83JxRLXoCqj9vrq4junnKqY3Z2Rju7BzqJaTWtmO4Rd_tbcTksPUhhbwOu7FdY7rDhK3L4zbi7ZPm0WBjwcv7_aL58u768_KmW318_2G5WHVOMDV33HrOB-nBatLr3qFSZFg7lAjWMhRCAaXeS62UkANx2lvgnnsAlNoJzS6at0fvdrce0TtM82Sj2U5htNMPk20wf_-ksDFf895UM4DgVfD8KMhlDqa4MKPbuJxSnYABRkHyQ5WXR2jzj_tmsTKHN0IJAUL1Hir74r6jKX_fYZnNGIrDGG3CvCuGEqhhcCbof1GQqgcllFIVfXVE3ZRLmXA4tQHEHDI3S_5p-SvzRYWf_TmUE_o7YfYTwgWltg</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1786185888</pqid></control><display><type>article</type><title>Electron localization in a mixed-valence diniobium benzene complex</title><source>DOAJ Directory of Open Access Journals</source><source>Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals</source><source>PubMed Central</source><source>PubMed Central Open Access</source><creator>Gianetti, Thomas L ; Nocton, Grégory ; Minasian, Stefan G ; Kaltsoyannis, Nikolas ; Kilcoyne, A L David ; Kozimor, Stosh A ; Shuh, David K ; Tyliszczak, Tolek ; Bergman, Robert G ; Arnold, John</creator><creatorcontrib>Gianetti, Thomas L ; Nocton, Grégory ; Minasian, Stefan G ; Kaltsoyannis, Nikolas ; Kilcoyne, A L David ; Kozimor, Stosh A ; Shuh, David K ; Tyliszczak, Tolek ; Bergman, Robert G ; Arnold, John ; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States) ; Los Alamos National Lab. (LANL), Los Alamos, NM (United States)</creatorcontrib><description>Reaction of the neutral diniobium benzene complex {[Nb(BDI)N
Bu]
(μ-C
H
)} (BDI =
,
'-diisopropylbenzene-β-diketiminate) with Ag[B(C
F
)
] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N
Bu]
(μ-C
H
)}{B(C
F
)
}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L
-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment of a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the δ-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/c4sc02705a</identifier><identifier>PMID: 29560186</identifier><language>eng</language><publisher>England: The Royal Society of Chemistry</publisher><subject>Asymmetry ; Atomic beam spectroscopy ; Atomic structure ; Benzene ; Chemical Sciences ; Chemistry ; Inorganic and Physical Chemistry ; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ; Niobium ; Niobium Benzene Comples ; Other ; Oxidation ; Single electrons ; X-rays</subject><ispartof>Chemical science (Cambridge), 2015-02, Vol.6 (2), p.993-1003</ispartof><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><rights>This journal is © The Royal Society of Chemistry 2014 2014</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c538t-4ad44f7d1a90696ce880fbce7e1aa3e558122dd798857f0c9da14d4d11e79c593</citedby><cites>FETCH-LOGICAL-c538t-4ad44f7d1a90696ce880fbce7e1aa3e558122dd798857f0c9da14d4d11e79c593</cites><orcidid>0000-0003-0599-1176</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC5811154/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC5811154/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,723,776,780,860,881,27901,27902,53766,53768</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/29560186$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-02001029$$DView record in HAL$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/servlets/purl/1321749$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Gianetti, Thomas L</creatorcontrib><creatorcontrib>Nocton, Grégory</creatorcontrib><creatorcontrib>Minasian, Stefan G</creatorcontrib><creatorcontrib>Kaltsoyannis, Nikolas</creatorcontrib><creatorcontrib>Kilcoyne, A L David</creatorcontrib><creatorcontrib>Kozimor, Stosh A</creatorcontrib><creatorcontrib>Shuh, David K</creatorcontrib><creatorcontrib>Tyliszczak, Tolek</creatorcontrib><creatorcontrib>Bergman, Robert G</creatorcontrib><creatorcontrib>Arnold, John</creatorcontrib><creatorcontrib>Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)</creatorcontrib><creatorcontrib>Los Alamos National Lab. (LANL), Los Alamos, NM (United States)</creatorcontrib><title>Electron localization in a mixed-valence diniobium benzene complex</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><description>Reaction of the neutral diniobium benzene complex {[Nb(BDI)N
Bu]
(μ-C
H
)} (BDI =
,
'-diisopropylbenzene-β-diketiminate) with Ag[B(C
F
)
] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N
Bu]
(μ-C
H
)}{B(C
F
)
}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L
-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment of a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the δ-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.</description><subject>Asymmetry</subject><subject>Atomic beam spectroscopy</subject><subject>Atomic structure</subject><subject>Benzene</subject><subject>Chemical Sciences</subject><subject>Chemistry</subject><subject>Inorganic and Physical Chemistry</subject><subject>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</subject><subject>Niobium</subject><subject>Niobium Benzene Comples</subject><subject>Other</subject><subject>Oxidation</subject><subject>Single electrons</subject><subject>X-rays</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNqFkU1vEzEQhlcIRKvSCz8ArTgB0oLHH2v7gpRGhSJF4gCcLceeJUZeO6w3UemvxyElAi744q9Hz4zmbZqnQF4DYfqN48URKomwD5pzSjh0vWD64elMyVlzWco3UhdjIKh83JxRLXoCqj9vrq4junnKqY3Z2Rju7BzqJaTWtmO4Rd_tbcTksPUhhbwOu7FdY7rDhK3L4zbi7ZPm0WBjwcv7_aL58u768_KmW318_2G5WHVOMDV33HrOB-nBatLr3qFSZFg7lAjWMhRCAaXeS62UkANx2lvgnnsAlNoJzS6at0fvdrce0TtM82Sj2U5htNMPk20wf_-ksDFf895UM4DgVfD8KMhlDqa4MKPbuJxSnYABRkHyQ5WXR2jzj_tmsTKHN0IJAUL1Hir74r6jKX_fYZnNGIrDGG3CvCuGEqhhcCbof1GQqgcllFIVfXVE3ZRLmXA4tQHEHDI3S_5p-SvzRYWf_TmUE_o7YfYTwgWltg</recordid><startdate>20150201</startdate><enddate>20150201</enddate><creator>Gianetti, Thomas L</creator><creator>Nocton, Grégory</creator><creator>Minasian, Stefan G</creator><creator>Kaltsoyannis, Nikolas</creator><creator>Kilcoyne, A L David</creator><creator>Kozimor, Stosh A</creator><creator>Shuh, David K</creator><creator>Tyliszczak, Tolek</creator><creator>Bergman, Robert G</creator><creator>Arnold, John</creator><general>The Royal Society of Chemistry</general><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><scope>1XC</scope><scope>OIOZB</scope><scope>OTOTI</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0003-0599-1176</orcidid></search><sort><creationdate>20150201</creationdate><title>Electron localization in a mixed-valence diniobium benzene complex</title><author>Gianetti, Thomas L ; Nocton, Grégory ; Minasian, Stefan G ; Kaltsoyannis, Nikolas ; Kilcoyne, A L David ; Kozimor, Stosh A ; Shuh, David K ; Tyliszczak, Tolek ; Bergman, Robert G ; Arnold, John</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c538t-4ad44f7d1a90696ce880fbce7e1aa3e558122dd798857f0c9da14d4d11e79c593</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Asymmetry</topic><topic>Atomic beam spectroscopy</topic><topic>Atomic structure</topic><topic>Benzene</topic><topic>Chemical Sciences</topic><topic>Chemistry</topic><topic>Inorganic and Physical Chemistry</topic><topic>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</topic><topic>Niobium</topic><topic>Niobium Benzene Comples</topic><topic>Other</topic><topic>Oxidation</topic><topic>Single electrons</topic><topic>X-rays</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Gianetti, Thomas L</creatorcontrib><creatorcontrib>Nocton, Grégory</creatorcontrib><creatorcontrib>Minasian, Stefan G</creatorcontrib><creatorcontrib>Kaltsoyannis, Nikolas</creatorcontrib><creatorcontrib>Kilcoyne, A L David</creatorcontrib><creatorcontrib>Kozimor, Stosh A</creatorcontrib><creatorcontrib>Shuh, David K</creatorcontrib><creatorcontrib>Tyliszczak, Tolek</creatorcontrib><creatorcontrib>Bergman, Robert G</creatorcontrib><creatorcontrib>Arnold, John</creatorcontrib><creatorcontrib>Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)</creatorcontrib><creatorcontrib>Los Alamos National Lab. (LANL), Los Alamos, NM (United States)</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>MEDLINE - Academic</collection><collection>Hyper Article en Ligne (HAL)</collection><collection>OSTI.GOV - Hybrid</collection><collection>OSTI.GOV</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Gianetti, Thomas L</au><au>Nocton, Grégory</au><au>Minasian, Stefan G</au><au>Kaltsoyannis, Nikolas</au><au>Kilcoyne, A L David</au><au>Kozimor, Stosh A</au><au>Shuh, David K</au><au>Tyliszczak, Tolek</au><au>Bergman, Robert G</au><au>Arnold, John</au><aucorp>Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)</aucorp><aucorp>Los Alamos National Lab. (LANL), Los Alamos, NM (United States)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Electron localization in a mixed-valence diniobium benzene complex</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2015-02-01</date><risdate>2015</risdate><volume>6</volume><issue>2</issue><spage>993</spage><epage>1003</epage><pages>993-1003</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>Reaction of the neutral diniobium benzene complex {[Nb(BDI)N
Bu]
(μ-C
H
)} (BDI =
,
'-diisopropylbenzene-β-diketiminate) with Ag[B(C
F
)
] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N
Bu]
(μ-C
H
)}{B(C
F
)
}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L
-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment of a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the δ-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.</abstract><cop>England</cop><pub>The Royal Society of Chemistry</pub><pmid>29560186</pmid><doi>10.1039/c4sc02705a</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0003-0599-1176</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 2041-6520 |
| ispartof | Chemical science (Cambridge), 2015-02, Vol.6 (2), p.993-1003 |
| issn | 2041-6520 2041-6539 |
| language | eng |
| recordid | cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_5811154 |
| source | DOAJ Directory of Open Access Journals; Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals; PubMed Central; PubMed Central Open Access |
| subjects | Asymmetry Atomic beam spectroscopy Atomic structure Benzene Chemical Sciences Chemistry Inorganic and Physical Chemistry INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Niobium Niobium Benzene Comples Other Oxidation Single electrons X-rays |
| title | Electron localization in a mixed-valence diniobium benzene complex |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-12T17%3A31%3A20IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_pubme&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Electron%20localization%20in%20a%20mixed-valence%20diniobium%20benzene%20complex&rft.jtitle=Chemical%20science%20(Cambridge)&rft.au=Gianetti,%20Thomas%20L&rft.aucorp=Lawrence%20Berkeley%20National%20Lab.%20(LBNL),%20Berkeley,%20CA%20(United%20States)&rft.date=2015-02-01&rft.volume=6&rft.issue=2&rft.spage=993&rft.epage=1003&rft.pages=993-1003&rft.issn=2041-6520&rft.eissn=2041-6539&rft_id=info:doi/10.1039/c4sc02705a&rft_dat=%3Cproquest_pubme%3E2016534352%3C/proquest_pubme%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=1786185888&rft_id=info:pmid/29560186&rfr_iscdi=true |