Charge-transfer bonding in metal–arene coordination
Identifieur interne : 003534 ( Istex/Corpus ); précédent : 003533; suivant : 003535Charge-transfer bonding in metal–arene coordination
Auteurs : Stephan M. Hubig ; Sergey V. Lindeman ; Jay K. KochiSource :
- Coordination Chemistry Reviews [ 0010-8545 ] ; 2000.
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Abstract
X-ray crystallographic structures of donor–acceptor complexes of aromatic hydrocarbons with transition metals are re-examined with the focus on the arene ligands. Thus, significant structural and electronic changes are revealed in the arene moiety due to coordination to the metal center including: (i) expansion of the aromatic six-carbon ring; (ii) endocyclic π-bond localization; (iii) distortion of the planarity (folding) of the arene ring; and (iv) shortening of the metalarene bond distances. All structural features are characteristic of metal–arene (π- or σ-) complexes that exhibit various degrees of (metal-to-ligand) charge transfer. The concept of charge-transfer bonding not only explains the structural details but also the various facets of chemical reactivity of metal-coordinated arenes including efficient carbonhydrogen bond activation and nucleophilic–electrophilic umpolung, both of which are critical factors in homogeneous metal catalysis.
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DOI: 10.1016/S0010-8545(00)00322-2
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Thus, significant structural and electronic changes are revealed in the arene moiety due to coordination to the metal center including: (i) expansion of the aromatic six-carbon ring; (ii) endocyclic π-bond localization; (iii) distortion of the planarity (folding) of the arene ring; and (iv) shortening of the metalarene bond distances. All structural features are characteristic of metal–arene (π- or σ-) complexes that exhibit various degrees of (metal-to-ligand) charge transfer. 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Tel.: +1-713-7433290; fax: +1-713-7432709</p></note><affiliation>Department of Chemistry, University of Houston, Houston, TX 77204-5641, USA</affiliation></author></analytic><monogr><title level="j">Coordination Chemistry Reviews</title><title level="j" type="abbrev">CCR</title><idno type="pISSN">0010-8545</idno><idno type="PII">S0010-8545(00)X0043-4</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="2000"></date><biblScope unit="volume">200–202</biblScope><biblScope unit="supplement">C</biblScope><biblScope unit="page" from="831">831</biblScope><biblScope unit="page" to="873">873</biblScope></imprint></monogr><idno type="istex">364532591AA61756D71F806E1991B6704D11E667</idno><idno type="DOI">10.1016/S0010-8545(00)00322-2</idno><idno type="PII">S0010-8545(00)00322-2</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>2000</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>X-ray crystallographic structures of donor–acceptor complexes of aromatic hydrocarbons with transition metals are re-examined with the focus on the arene ligands. Thus, significant structural and electronic changes are revealed in the arene moiety due to coordination to the metal center including: (i) expansion of the aromatic six-carbon ring; (ii) endocyclic π-bond localization; (iii) distortion of the planarity (folding) of the arene ring; and (iv) shortening of the metalarene bond distances. All structural features are characteristic of metal–arene (π- or σ-) complexes that exhibit various degrees of (metal-to-ligand) charge transfer. 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name="fx41"></istex:entity><istex:entity SYSTEM="fx42" NDATA="IMAGE" name="fx42"></istex:entity></istex:docType><istex:document><converted-article version="4.5.2" docsubtype="rev" xml:lang="en"><item-info><jid>CCR</jid><aid>9771</aid><ce:pii>S0010-8545(00)00322-2</ce:pii><ce:doi>10.1016/S0010-8545(00)00322-2</ce:doi><ce:copyright type="full-transfer" year="2000">Elsevier Science S.A.</ce:copyright></item-info><head><ce:title>Charge-transfer bonding in metal–arene coordination</ce:title><ce:author-group><ce:author><ce:given-name>Stephan M</ce:given-name><ce:surname>Hubig</ce:surname></ce:author><ce:author><ce:given-name>Sergey V</ce:given-name><ce:surname>Lindeman</ce:surname></ce:author><ce:author><ce:given-name>Jay K</ce:given-name><ce:surname>Kochi</ce:surname><ce:cross-ref refid="CORR1">*</ce:cross-ref><ce:e-address>jkochi@pop.uh.edu</ce:e-address></ce:author><ce:affiliation><ce:textfn>Department of Chemistry, University of Houston, Houston, TX 77204-5641, USA</ce:textfn></ce:affiliation><ce:correspondence id="CORR1"><ce:label>*</ce:label><ce:text>Corresponding author. Tel.: +1-713-7433290; fax: +1-713-7432709</ce:text></ce:correspondence></ce:author-group><ce:date-received day="23" month="9" year="1999"></ce:date-received><ce:date-accepted day="23" month="2" year="2000"></ce:date-accepted><ce:abstract><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>X-ray crystallographic structures of donor–acceptor complexes of aromatic hydrocarbons with transition metals are re-examined with the focus on the arene ligands. Thus, significant structural and electronic changes are revealed in the arene moiety due to coordination to the metal center including: (i) expansion of the aromatic six-carbon ring; (ii) endocyclic π-bond localization; (iii) distortion of the planarity (folding) of the arene ring; and (iv) shortening of the metalarene bond distances. All structural features are characteristic of metal–arene (π- or σ-) complexes that exhibit various degrees of (metal-to-ligand) charge transfer. The concept of charge-transfer bonding not only explains the structural details but also the various facets of chemical reactivity of metal-coordinated arenes including efficient carbonhydrogen bond activation and nucleophilic–electrophilic <ce:italic>umpolung</ce:italic>, both of which are critical factors in homogeneous metal catalysis.</ce:simple-para></ce:abstract-sec></ce:abstract><ce:keywords class="keyword"><ce:section-title>Keywords</ce:section-title><ce:keyword><ce:text>Metal–arene coordination</ce:text></ce:keyword><ce:keyword><ce:text>Donor–acceptor complex</ce:text></ce:keyword><ce:keyword><ce:text>Charge-transfer bonding</ce:text></ce:keyword><ce:keyword><ce:text>Electrophilic–nucleophilic <ce:italic>umpolung</ce:italic></ce:text></ce:keyword><ce:keyword><ce:text>CH bond activation</ce:text></ce:keyword><ce:keyword><ce:text>X-ray structures</ce:text></ce:keyword></ce:keywords></head></converted-article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Charge-transfer bonding in metal–arene coordination</title></titleInfo><titleInfo type="alternative" lang="en" contentType="CDATA"><title>Charge-transfer bonding in metal–arene coordination</title></titleInfo><name type="personal"><namePart type="given">Stephan M</namePart><namePart type="family">Hubig</namePart><affiliation>Department of Chemistry, University of Houston, Houston, TX 77204-5641, USA</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Sergey V</namePart><namePart type="family">Lindeman</namePart><affiliation>Department of Chemistry, University of Houston, Houston, TX 77204-5641, USA</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Jay K</namePart><namePart type="family">Kochi</namePart><affiliation>Department of Chemistry, University of Houston, Houston, TX 77204-5641, USA</affiliation><affiliation>E-mail: jkochi@pop.uh.edu</affiliation><description>Corresponding author. Tel.: +1-713-7433290; fax: +1-713-7432709</description><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="review-article" displayLabel="Review article"></genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">2000</dateIssued><dateValid encoding="w3cdtf">2000-02-23</dateValid><copyrightDate encoding="w3cdtf">2000</copyrightDate></originInfo><language><languageTerm type="code" authority="iso639-2b">eng</languageTerm><languageTerm type="code" authority="rfc3066">en</languageTerm></language><physicalDescription><internetMediaType>text/html</internetMediaType></physicalDescription><abstract lang="en">X-ray crystallographic structures of donor–acceptor complexes of aromatic hydrocarbons with transition metals are re-examined with the focus on the arene ligands. Thus, significant structural and electronic changes are revealed in the arene moiety due to coordination to the metal center including: (i) expansion of the aromatic six-carbon ring; (ii) endocyclic π-bond localization; (iii) distortion of the planarity (folding) of the arene ring; and (iv) shortening of the metalarene bond distances. All structural features are characteristic of metal–arene (π- or σ-) complexes that exhibit various degrees of (metal-to-ligand) charge transfer. The concept of charge-transfer bonding not only explains the structural details but also the various facets of chemical reactivity of metal-coordinated arenes including efficient carbonhydrogen bond activation and nucleophilic–electrophilic umpolung, both of which are critical factors in homogeneous metal catalysis.</abstract><note type="content">Scheme 1: </note><note type="content">Scheme 2: </note><note type="content">Scheme 3: </note><note type="content">Scheme 4: </note><note type="content">Scheme 5: </note><note type="content">Scheme 6: </note><note type="content">Scheme 7: </note><note type="content">Scheme 8: </note><note type="content">Scheme 9: </note><note type="content">Scheme 10: </note><note type="content">Scheme 11: </note><note type="content">Scheme 12: </note><note type="content">Scheme 13: </note><note type="content">Fig. 1: Stacking of the crystalline EDA complex of bis(hexamethylbenzene) iron(II) with durene (donor–acceptor distance d=3.65 Å).</note><note type="content">Scheme 14: </note><note type="content">Scheme 15: </note><note type="content">Scheme 16: </note><note type="content">Scheme 17: </note><note type="content">Scheme 18: </note><note type="content">Scheme 19: </note><note type="content">Scheme 20: </note><note type="content">Scheme 21: </note><note type="content">Scheme 22: </note><note type="content">Scheme 23: </note><note type="content">Scheme 24: </note><note type="content">Scheme 25: </note><note type="content">Scheme 26: </note><note type="content">Scheme 27: </note><note type="content">Table 1: Relationship between bond order and bond distance in the benzene ringa</note><note type="content">Table 2: Ionization potentials (IP) of various substituted benzenes</note><note type="content">Table 3: Average geometrical parameters (Å/°) of η1-coordinated arene complexes</note><note type="content">Table 4: Average geometrical parameters (Å/°) of η2-coordinated arene complexes</note><subject lang="en"><genre>Keywords</genre><topic>Metal–arene coordination</topic><topic>Donor–acceptor complex</topic><topic>Charge-transfer bonding</topic><topic>Electrophilic–nucleophilic umpolung</topic><topic>CH bond activation</topic><topic>X-ray structures</topic></subject><relatedItem type="host"><titleInfo><title>Coordination Chemistry Reviews</title></titleInfo><titleInfo type="abbreviated"><title>CCR</title></titleInfo><genre type="Journal">journal</genre><originInfo><dateIssued encoding="w3cdtf">200005</dateIssued></originInfo><identifier type="ISSN">0010-8545</identifier><identifier type="PII">S0010-8545(00)X0043-4</identifier><part><date>200005</date><detail type="volume"><number>200–202</number><caption>vol.</caption></detail><detail type="supplement"><number>C</number><caption>Suppl.</caption></detail><extent unit="issue pages"><start>1</start><end>1040</end></extent><extent unit="pages"><start>831</start><end>873</end></extent></part></relatedItem><identifier type="istex">364532591AA61756D71F806E1991B6704D11E667</identifier><identifier type="DOI">10.1016/S0010-8545(00)00322-2</identifier><identifier type="PII">S0010-8545(00)00322-2</identifier><accessCondition type="use and reproduction" contentType="">© 2000Elsevier Science S.A.</accessCondition><recordInfo><recordContentSource>ELSEVIER</recordContentSource><recordOrigin>Elsevier Science S.A., ©2000</recordOrigin></recordInfo></mods></metadata><enrichments><istex:catWosTEI uri="https://api.istex.fr/document/364532591AA61756D71F806E1991B6704D11E667/enrichments/catWos"><teiHeader><profileDesc><textClass><classCode scheme="WOS">CHEMISTRY, INORGANIC & NUCLEAR</classCode></textClass></profileDesc></teiHeader></istex:catWosTEI></enrichments><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
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