Experimental Determination of the Electron Density Topology in a Non-centrosymmetric Transition Metal Complex:  [Ni(H3L)][NO3][PF6] [H3L = N,N‘,N‘‘-Tris(2-hydroxy-3-methylbutyl)-1,4,7-triazacyclononane]

Experimental Determination of the Electron Density Topology in a Non-centrosymmetric Transition Metal Complex:  [Ni(H3L)][NO3][PF6] [H3L = N,N‘,N‘‘-Tris(2-hydroxy-3-methylbutyl)-1,4,7-triazacyclononane]

We have determined the experimental charge density of the title compound, a large pendant arm macrocyclic complex, by fitting a multipole model to high-resolution X-ray diffraction data. We find redistribution of the charge density from the ligating nitrogen and oxygen atoms to the central nickel io...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Journal of the American Chemical Society 1997-05, Vol.119 (21), p.5028-5034
Hauptverfasser: Smith, G. T, Mallinson, P. R, Frampton, C. S, Farrugia, L. J, Peacock, R. D, Howard, J. A. K
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 5034
container_issue 21
container_start_page 5028
container_title Journal of the American Chemical Society
container_volume 119
creator Smith, G. T
Mallinson, P. R
Frampton, C. S
Farrugia, L. J
Peacock, R. D
Howard, J. A. K
description We have determined the experimental charge density of the title compound, a large pendant arm macrocyclic complex, by fitting a multipole model to high-resolution X-ray diffraction data. We find redistribution of the charge density from the ligating nitrogen and oxygen atoms to the central nickel ion which considerably reduces the charge on the metal. While the d-orbital populations are in agreement with ligand-field theory, the charge density of the metal shows diffuse features which are ascribed to metal 4s and 4p participation in the metal−ligand bonding. Additionally, the trigonal-planar arrangement of critical points in −∇2ρ(r) within the valence shell charge concentration (VSCC) of the ligating oxygen atom provides evidence for metal−oxygen π-bonding.
doi_str_mv 10.1021/ja964264q
format Article
fullrecord <record><control><sourceid>acs_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1021_ja964264q</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>b875404236</sourcerecordid><originalsourceid>FETCH-LOGICAL-a361t-9abb62f0a1c68329eef6d18a9e9ef3f436fe1c0c60afe68db06cdc46eeb4ed5d3</originalsourceid><addsrcrecordid>eNptkd1q2zAUgM3YYFm3i72BbgYNRJt-bMUe7GKkaTvI3EA9ehGCkeXjxZktZbIK0a562zfoc-0R-iRTltGrgTjiHD59h6MTRW8peU8Jox-2MhMxE_HPZ9GIJozghDLxPBoRQhiepoK_jF4NwzakMUvpKPo93-_Atj1oJzt0Bg5s32rpWqORaZDbAJp3oJwN-RnooXUeFWZnOvPdo1YjiXKjsQrPrRl834OzrUKFlQf0IPkKB_HM9LsO9h8f7-7RKm9PL_livF7lV3y9Wp6LNVqFAvqE8kn-ePfwN4SDC9sOpwxvfG3N3mOOg37ju-rW-W6M6SSeTHHoJ39J5VVntNFSw_p19KKR3QBv_t0n0bfzeTG7xIuriy-zzwssuaAOZ7KqBGuIpEqknGUAjahpKjPIoOFNzEUDVBEliGxApHVFhKpVLACqGOqk5ifR-OhVYfTBQlPuwkdK60tKysMyyqdlBBYf2XZwsH8Cpf1RiimfJmWxvC5vLpJlRhc35XXg3x15qYZya26tDpP8x_sHXgae3A</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Experimental Determination of the Electron Density Topology in a Non-centrosymmetric Transition Metal Complex:  [Ni(H3L)][NO3][PF6] [H3L = N,N‘,N‘‘-Tris(2-hydroxy-3-methylbutyl)-1,4,7-triazacyclononane]</title><source>ACS Publications</source><creator>Smith, G. T ; Mallinson, P. R ; Frampton, C. S ; Farrugia, L. J ; Peacock, R. D ; Howard, J. A. K</creator><creatorcontrib>Smith, G. T ; Mallinson, P. R ; Frampton, C. S ; Farrugia, L. J ; Peacock, R. D ; Howard, J. A. K</creatorcontrib><description>We have determined the experimental charge density of the title compound, a large pendant arm macrocyclic complex, by fitting a multipole model to high-resolution X-ray diffraction data. We find redistribution of the charge density from the ligating nitrogen and oxygen atoms to the central nickel ion which considerably reduces the charge on the metal. While the d-orbital populations are in agreement with ligand-field theory, the charge density of the metal shows diffuse features which are ascribed to metal 4s and 4p participation in the metal−ligand bonding. Additionally, the trigonal-planar arrangement of critical points in −∇2ρ(r) within the valence shell charge concentration (VSCC) of the ligating oxygen atom provides evidence for metal−oxygen π-bonding.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja964264q</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Journal of the American Chemical Society, 1997-05, Vol.119 (21), p.5028-5034</ispartof><rights>Copyright © 1997 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a361t-9abb62f0a1c68329eef6d18a9e9ef3f436fe1c0c60afe68db06cdc46eeb4ed5d3</citedby><cites>FETCH-LOGICAL-a361t-9abb62f0a1c68329eef6d18a9e9ef3f436fe1c0c60afe68db06cdc46eeb4ed5d3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja964264q$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja964264q$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2751,27055,27903,27904,56716,56766</link.rule.ids></links><search><creatorcontrib>Smith, G. T</creatorcontrib><creatorcontrib>Mallinson, P. R</creatorcontrib><creatorcontrib>Frampton, C. S</creatorcontrib><creatorcontrib>Farrugia, L. J</creatorcontrib><creatorcontrib>Peacock, R. D</creatorcontrib><creatorcontrib>Howard, J. A. K</creatorcontrib><title>Experimental Determination of the Electron Density Topology in a Non-centrosymmetric Transition Metal Complex:  [Ni(H3L)][NO3][PF6] [H3L = N,N‘,N‘‘-Tris(2-hydroxy-3-methylbutyl)-1,4,7-triazacyclononane]</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>We have determined the experimental charge density of the title compound, a large pendant arm macrocyclic complex, by fitting a multipole model to high-resolution X-ray diffraction data. We find redistribution of the charge density from the ligating nitrogen and oxygen atoms to the central nickel ion which considerably reduces the charge on the metal. While the d-orbital populations are in agreement with ligand-field theory, the charge density of the metal shows diffuse features which are ascribed to metal 4s and 4p participation in the metal−ligand bonding. Additionally, the trigonal-planar arrangement of critical points in −∇2ρ(r) within the valence shell charge concentration (VSCC) of the ligating oxygen atom provides evidence for metal−oxygen π-bonding.</description><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1997</creationdate><recordtype>article</recordtype><recordid>eNptkd1q2zAUgM3YYFm3i72BbgYNRJt-bMUe7GKkaTvI3EA9ehGCkeXjxZktZbIK0a562zfoc-0R-iRTltGrgTjiHD59h6MTRW8peU8Jox-2MhMxE_HPZ9GIJozghDLxPBoRQhiepoK_jF4NwzakMUvpKPo93-_Atj1oJzt0Bg5s32rpWqORaZDbAJp3oJwN-RnooXUeFWZnOvPdo1YjiXKjsQrPrRl834OzrUKFlQf0IPkKB_HM9LsO9h8f7-7RKm9PL_livF7lV3y9Wp6LNVqFAvqE8kn-ePfwN4SDC9sOpwxvfG3N3mOOg37ju-rW-W6M6SSeTHHoJ39J5VVntNFSw_p19KKR3QBv_t0n0bfzeTG7xIuriy-zzwssuaAOZ7KqBGuIpEqknGUAjahpKjPIoOFNzEUDVBEliGxApHVFhKpVLACqGOqk5ifR-OhVYfTBQlPuwkdK60tKysMyyqdlBBYf2XZwsH8Cpf1RiimfJmWxvC5vLpJlRhc35XXg3x15qYZya26tDpP8x_sHXgae3A</recordid><startdate>19970528</startdate><enddate>19970528</enddate><creator>Smith, G. T</creator><creator>Mallinson, P. R</creator><creator>Frampton, C. S</creator><creator>Farrugia, L. J</creator><creator>Peacock, R. D</creator><creator>Howard, J. A. K</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19970528</creationdate><title>Experimental Determination of the Electron Density Topology in a Non-centrosymmetric Transition Metal Complex:  [Ni(H3L)][NO3][PF6] [H3L = N,N‘,N‘‘-Tris(2-hydroxy-3-methylbutyl)-1,4,7-triazacyclononane]</title><author>Smith, G. T ; Mallinson, P. R ; Frampton, C. S ; Farrugia, L. J ; Peacock, R. D ; Howard, J. A. K</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a361t-9abb62f0a1c68329eef6d18a9e9ef3f436fe1c0c60afe68db06cdc46eeb4ed5d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1997</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Smith, G. T</creatorcontrib><creatorcontrib>Mallinson, P. R</creatorcontrib><creatorcontrib>Frampton, C. S</creatorcontrib><creatorcontrib>Farrugia, L. J</creatorcontrib><creatorcontrib>Peacock, R. D</creatorcontrib><creatorcontrib>Howard, J. A. K</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Smith, G. T</au><au>Mallinson, P. R</au><au>Frampton, C. S</au><au>Farrugia, L. J</au><au>Peacock, R. D</au><au>Howard, J. A. K</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Experimental Determination of the Electron Density Topology in a Non-centrosymmetric Transition Metal Complex:  [Ni(H3L)][NO3][PF6] [H3L = N,N‘,N‘‘-Tris(2-hydroxy-3-methylbutyl)-1,4,7-triazacyclononane]</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>1997-05-28</date><risdate>1997</risdate><volume>119</volume><issue>21</issue><spage>5028</spage><epage>5034</epage><pages>5028-5034</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>We have determined the experimental charge density of the title compound, a large pendant arm macrocyclic complex, by fitting a multipole model to high-resolution X-ray diffraction data. We find redistribution of the charge density from the ligating nitrogen and oxygen atoms to the central nickel ion which considerably reduces the charge on the metal. While the d-orbital populations are in agreement with ligand-field theory, the charge density of the metal shows diffuse features which are ascribed to metal 4s and 4p participation in the metal−ligand bonding. Additionally, the trigonal-planar arrangement of critical points in −∇2ρ(r) within the valence shell charge concentration (VSCC) of the ligating oxygen atom provides evidence for metal−oxygen π-bonding.</abstract><pub>American Chemical Society</pub><doi>10.1021/ja964264q</doi><tpages>7</tpages></addata></record>
fulltext fulltext
identifier ISSN: 0002-7863
ispartof Journal of the American Chemical Society, 1997-05, Vol.119 (21), p.5028-5034
issn 0002-7863
1520-5126
language eng
recordid cdi_crossref_primary_10_1021_ja964264q
source ACS Publications
title Experimental Determination of the Electron Density Topology in a Non-centrosymmetric Transition Metal Complex:  [Ni(H3L)][NO3][PF6] [H3L = N,N‘,N‘‘-Tris(2-hydroxy-3-methylbutyl)-1,4,7-triazacyclononane]
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-24T08%3A01%3A37IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-acs_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Experimental%20Determination%20of%20the%20Electron%20Density%20Topology%20in%20a%20Non-centrosymmetric%20Transition%20Metal%20Complex:%E2%80%89%20%5BNi(H3L)%5D%5BNO3%5D%5BPF6%5D%20%5BH3L%20=%20N,N%E2%80%98,N%E2%80%98%E2%80%98-Tris(2-hydroxy-3-methylbutyl)-1,4,7-triazacyclononane%5D&rft.jtitle=Journal%20of%20the%20American%20Chemical%20Society&rft.au=Smith,%20G.%20T&rft.date=1997-05-28&rft.volume=119&rft.issue=21&rft.spage=5028&rft.epage=5034&rft.pages=5028-5034&rft.issn=0002-7863&rft.eissn=1520-5126&rft_id=info:doi/10.1021/ja964264q&rft_dat=%3Cacs_cross%3Eb875404236%3C/acs_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/&rfr_iscdi=true