Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of cis , trans -bis(2-dimethyl-aminoethyl)-diphenyl-phosphino(dichloro)ruthenium(II)
Identifieur interne : 002869 ( Istex/Corpus ); précédent : 002868; suivant : 002870Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of cis , trans -bis(2-dimethyl-aminoethyl)-diphenyl-phosphino(dichloro)ruthenium(II)
Auteurs : Zijian Guo ; Abraha Habtemariam ; Peter J. Sadler ; Brian R. JamesSource :
- Inorganica Chimica Acta [ 0020-1693 ] ; 1998.
English descriptors
Abstract
Abstract: The Ru(II) complex cis,trans-[Ru(Me2NCH2CH2PPh2-P,N)2Cl2] (1) has been characterized in the solid state and in solution. X-ray crystallography showed that complex 1 is monoclinic, space group C2/c; a = 36.0421, b = 11.4866, c = 31.0540 Å; β = 104.556°. The structure refined to R = 0.0925 and Rw = 0.223. There are two independent molecules in the unit cell, with normal Ru-P bonds (2.24–2.26 Å), but the Ru-N bonds (2.37–2.42 Å) are 0.2 Å longer than typical values for Ru-N trans to phosphorus. The Cl-Ru-Cl bond angles of 1 are 171.78 and 173.14°. Complex 1 is stable in methylene chloride solution and cyclic voltammetry showed that it undergoes a fully reversible one-electron oxidation at 0.326 V. In methanol, however, 1 (both in air or under N2) undergoes a two-stage ionization/solvolysis with first order constants at 293 K: 5.40 ± 0.02 × 10−4 s−1 for the first step, and 3.29 ± 0.03 × 10−5 s−1 for the second step accompanied by a colour change from red to green. 1H and 31P{1H} NMR spectroscopic studies suggest that the solvolysis is accompanied by P,N-chelate ring-opening. These processes are inhibited by the presence of excess of lithium chloride.
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DOI: 10.1016/S0020-1693(97)05911-2
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<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title xml:lang="en">Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of cis , trans -bis(2-dimethyl-aminoethyl)-diphenyl-phosphino(dichloro)ruthenium(II)</title><author><name sortKey="Guo, Zijian" sort="Guo, Zijian" uniqKey="Guo Z" first="Zijian" last="Guo">Zijian Guo</name><affiliation><mods:affiliation>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</mods:affiliation></affiliation></author><author><name sortKey="Habtemariam, Abraha" sort="Habtemariam, Abraha" uniqKey="Habtemariam A" first="Abraha" last="Habtemariam">Abraha Habtemariam</name><affiliation><mods:affiliation>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</mods:affiliation></affiliation></author><author><name sortKey="Sadler, Peter J" sort="Sadler, Peter J" uniqKey="Sadler P" first="Peter J." last="Sadler">Peter J. Sadler</name><affiliation><mods:affiliation>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</mods:affiliation></affiliation><affiliation><mods:affiliation>Corresponding author. Tel.: +44 131 650 4729; fax: +44 131 650 6542;</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: P.J.@ed.ac.uk</mods:affiliation></affiliation></author><author><name sortKey="James, Brian R" sort="James, Brian R" uniqKey="James B" first="Brian R." last="James">Brian R. James</name><affiliation><mods:affiliation>Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1ZI, Canada</mods:affiliation></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:D2884690EA5D10E7574042D63947CB0A1748D3C4</idno><date when="1998" year="1998">1998</date><idno type="doi">10.1016/S0020-1693(97)05911-2</idno><idno type="url">https://api-v5.istex.fr/document/D2884690EA5D10E7574042D63947CB0A1748D3C4/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">002869</idno><idno type="wicri:explorRef" wicri:stream="Istex" wicri:step="Corpus" wicri:corpus="ISTEX">002869</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a" type="main" xml:lang="en">Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of cis , trans -bis(2-dimethyl-aminoethyl)-diphenyl-phosphino(dichloro)ruthenium(II)</title><author><name sortKey="Guo, Zijian" sort="Guo, Zijian" uniqKey="Guo Z" first="Zijian" last="Guo">Zijian Guo</name><affiliation><mods:affiliation>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</mods:affiliation></affiliation></author><author><name sortKey="Habtemariam, Abraha" sort="Habtemariam, Abraha" uniqKey="Habtemariam A" first="Abraha" last="Habtemariam">Abraha Habtemariam</name><affiliation><mods:affiliation>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</mods:affiliation></affiliation></author><author><name sortKey="Sadler, Peter J" sort="Sadler, Peter J" uniqKey="Sadler P" first="Peter J." last="Sadler">Peter J. Sadler</name><affiliation><mods:affiliation>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</mods:affiliation></affiliation><affiliation><mods:affiliation>Corresponding author. Tel.: +44 131 650 4729; fax: +44 131 650 6542;</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: P.J.@ed.ac.uk</mods:affiliation></affiliation></author><author><name sortKey="James, Brian R" sort="James, Brian R" uniqKey="James B" first="Brian R." last="James">Brian R. James</name><affiliation><mods:affiliation>Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1ZI, Canada</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Inorganica Chimica Acta</title><title level="j" type="abbrev">ICA</title><idno type="ISSN">0020-1693</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1998">1998</date><biblScope unit="volume">273</biblScope><biblScope unit="issue">1–2</biblScope><biblScope unit="page" from="1">1</biblScope><biblScope unit="page" to="7">7</biblScope></imprint><idno type="ISSN">0020-1693</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0020-1693</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Aminophosphine complexes</term><term>Chelate ring complexes</term><term>Crystal structures</term><term>Ruthenium complexes</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Abstract: The Ru(II) complex cis,trans-[Ru(Me2NCH2CH2PPh2-P,N)2Cl2] (1) has been characterized in the solid state and in solution. X-ray crystallography showed that complex 1 is monoclinic, space group C2/c; a = 36.0421, b = 11.4866, c = 31.0540 Å; β = 104.556°. The structure refined to R = 0.0925 and Rw = 0.223. There are two independent molecules in the unit cell, with normal Ru-P bonds (2.24–2.26 Å), but the Ru-N bonds (2.37–2.42 Å) are 0.2 Å longer than typical values for Ru-N trans to phosphorus. The Cl-Ru-Cl bond angles of 1 are 171.78 and 173.14°. Complex 1 is stable in methylene chloride solution and cyclic voltammetry showed that it undergoes a fully reversible one-electron oxidation at 0.326 V. In methanol, however, 1 (both in air or under N2) undergoes a two-stage ionization/solvolysis with first order constants at 293 K: 5.40 ± 0.02 × 10−4 s−1 for the first step, and 3.29 ± 0.03 × 10−5 s−1 for the second step accompanied by a colour change from red to green. 1H and 31P{1H} NMR spectroscopic studies suggest that the solvolysis is accompanied by P,N-chelate ring-opening. These processes are inhibited by the presence of excess of lithium chloride.</div></front></TEI><istex><corpusName>elsevier</corpusName><author><json:item><name>Zijian Guo</name><affiliations><json:string>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</json:string></affiliations></json:item><json:item><name>Abraha Habtemariam</name><affiliations><json:string>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</json:string></affiliations></json:item><json:item><name>Peter J. Sadler</name><affiliations><json:string>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</json:string><json:string>Corresponding author. Tel.: +44 131 650 4729; fax: +44 131 650 6542;</json:string><json:string>E-mail: P.J.@ed.ac.uk</json:string></affiliations></json:item><json:item><name>Brian R. James</name><affiliations><json:string>Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1ZI, Canada</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>Ruthenium complexes</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Aminophosphine complexes</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Crystal structures</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Chelate ring complexes</value></json:item></subject><articleId><json:string>97059112</json:string></articleId><language><json:string>eng</json:string></language><originalGenre><json:string>Full-length article</json:string></originalGenre><abstract>Abstract: The Ru(II) complex cis,trans-[Ru(Me2NCH2CH2PPh2-P,N)2Cl2] (1) has been characterized in the solid state and in solution. X-ray crystallography showed that complex 1 is monoclinic, space group C2/c; a = 36.0421, b = 11.4866, c = 31.0540 Å; β = 104.556°. The structure refined to R = 0.0925 and Rw = 0.223. There are two independent molecules in the unit cell, with normal Ru-P bonds (2.24–2.26 Å), but the Ru-N bonds (2.37–2.42 Å) are 0.2 Å longer than typical values for Ru-N trans to phosphorus. The Cl-Ru-Cl bond angles of 1 are 171.78 and 173.14°. Complex 1 is stable in methylene chloride solution and cyclic voltammetry showed that it undergoes a fully reversible one-electron oxidation at 0.326 V. In methanol, however, 1 (both in air or under N2) undergoes a two-stage ionization/solvolysis with first order constants at 293 K: 5.40 ± 0.02 × 10−4 s−1 for the first step, and 3.29 ± 0.03 × 10−5 s−1 for the second step accompanied by a colour change from red to green. 1H and 31P{1H} NMR spectroscopic studies suggest that the solvolysis is accompanied by P,N-chelate ring-opening. These processes are inhibited by the presence of excess of lithium chloride.</abstract><qualityIndicators><score>6.277</score><pdfWordCount>3937</pdfWordCount><pdfCharCount>25422</pdfCharCount><pdfVersion>1.3</pdfVersion><pdfPageCount>7</pdfPageCount><pdfPageSize>598 x 771 pts</pdfPageSize><refBibsNative>true</refBibsNative><abstractWordCount>195</abstractWordCount><abstractCharCount>1178</abstractCharCount><keywordCount>4</keywordCount></qualityIndicators><title>Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of cis , trans -bis(2-dimethyl-aminoethyl)-diphenyl-phosphino(dichloro)ruthenium(II)</title><pii><json:string>S0020-1693(97)05911-2</json:string></pii><genre><json:string>research-article</json:string></genre><host><title>Inorganica Chimica Acta</title><language><json:string>unknown</json:string></language><publicationDate>1998</publicationDate><issn><json:string>0020-1693</json:string></issn><pii><json:string>S0020-1693(00)X0592-0</json:string></pii><volume>273</volume><issue>1–2</issue><pages><first>1</first><last>7</last></pages><genre><json:string>journal</json:string></genre></host><categories><wos><json:string>science</json:string><json:string>chemistry, inorganic & nuclear</json:string></wos><scienceMetrix><json:string>natural sciences</json:string><json:string>chemistry</json:string><json:string>inorganic & nuclear chemistry</json:string></scienceMetrix><inist><json:string>sciences appliquees, technologies et medecines</json:string><json:string>sciences biologiques et medicales</json:string><json:string>sciences biologiques fondamentales et appliquees. psychologie</json:string><json:string>vertebres: reproduction</json:string></inist></categories><publicationDate>1998</publicationDate><copyrightDate>1998</copyrightDate><doi><json:string>10.1016/S0020-1693(97)05911-2</json:string></doi><id>D2884690EA5D10E7574042D63947CB0A1748D3C4</id><fulltext><json:item><extension>pdf</extension><original>true</original><mimetype>application/pdf</mimetype><uri>https://api-v5.istex.fr/document/D2884690EA5D10E7574042D63947CB0A1748D3C4/fulltext/pdf</uri></json:item><json:item><extension>zip</extension><original>false</original><mimetype>application/zip</mimetype><uri>https://api-v5.istex.fr/document/D2884690EA5D10E7574042D63947CB0A1748D3C4/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api-v5.istex.fr/document/D2884690EA5D10E7574042D63947CB0A1748D3C4/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of cis , trans -bis(2-dimethyl-aminoethyl)-diphenyl-phosphino(dichloro)ruthenium(II)</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>ELSEVIER</publisher><availability><p>©1998 Elsevier Science S.A. All rights reserved.</p></availability><date>1998</date></publicationStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a" type="main" xml:lang="en">Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of cis , trans -bis(2-dimethyl-aminoethyl)-diphenyl-phosphino(dichloro)ruthenium(II)</title><author xml:id="author-0000"><persName><forename type="first">Zijian</forename><surname>Guo</surname></persName><affiliation>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</affiliation></author><author xml:id="author-0001"><persName><forename type="first">Abraha</forename><surname>Habtemariam</surname></persName><affiliation>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</affiliation></author><author xml:id="author-0002"><persName><forename type="first">Peter J.</forename><surname>Sadler</surname></persName><email>P.J.@ed.ac.uk</email><affiliation>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</affiliation><affiliation>Corresponding author. Tel.: +44 131 650 4729; fax: +44 131 650 6542;</affiliation></author><author xml:id="author-0003"><persName><forename type="first">Brian R.</forename><surname>James</surname></persName><affiliation>Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1ZI, Canada</affiliation></author><idno type="istex">D2884690EA5D10E7574042D63947CB0A1748D3C4</idno><idno type="DOI">10.1016/S0020-1693(97)05911-2</idno><idno type="PII">S0020-1693(97)05911-2</idno><idno type="ArticleID">97059112</idno></analytic><monogr><title level="j">Inorganica Chimica Acta</title><title level="j" type="abbrev">ICA</title><idno type="pISSN">0020-1693</idno><idno type="PII">S0020-1693(00)X0592-0</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1998"></date><biblScope unit="volume">273</biblScope><biblScope unit="issue">1–2</biblScope><biblScope unit="page" from="1">1</biblScope><biblScope unit="page" to="7">7</biblScope></imprint></monogr></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>1998</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>Abstract: The Ru(II) complex cis,trans-[Ru(Me2NCH2CH2PPh2-P,N)2Cl2] (1) has been characterized in the solid state and in solution. X-ray crystallography showed that complex 1 is monoclinic, space group C2/c; a = 36.0421, b = 11.4866, c = 31.0540 Å; β = 104.556°. The structure refined to R = 0.0925 and Rw = 0.223. There are two independent molecules in the unit cell, with normal Ru-P bonds (2.24–2.26 Å), but the Ru-N bonds (2.37–2.42 Å) are 0.2 Å longer than typical values for Ru-N trans to phosphorus. The Cl-Ru-Cl bond angles of 1 are 171.78 and 173.14°. Complex 1 is stable in methylene chloride solution and cyclic voltammetry showed that it undergoes a fully reversible one-electron oxidation at 0.326 V. In methanol, however, 1 (both in air or under N2) undergoes a two-stage ionization/solvolysis with first order constants at 293 K: 5.40 ± 0.02 × 10−4 s−1 for the first step, and 3.29 ± 0.03 × 10−5 s−1 for the second step accompanied by a colour change from red to green. 1H and 31P{1H} NMR spectroscopic studies suggest that the solvolysis is accompanied by P,N-chelate ring-opening. These processes are inhibited by the presence of excess of lithium chloride.</p></abstract><textClass xml:lang="en"><keywords scheme="keyword"><list><head>Keywords</head><item><term>Ruthenium complexes</term></item><item><term>Aminophosphine complexes</term></item><item><term>Crystal structures</term></item><item><term>Chelate ring complexes</term></item></list></keywords></textClass></profileDesc><revisionDesc><change when="1997-05-22">Modified</change><change when="1998">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><extension>txt</extension><original>false</original><mimetype>text/plain</mimetype><uri>https://api-v5.istex.fr/document/D2884690EA5D10E7574042D63947CB0A1748D3C4/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Elsevier doc found" wicri:toSee="Elsevier, no converted or simple article"><istex:xmlDeclaration>version="1.0" encoding="utf-8"</istex:xmlDeclaration><istex:docType PUBLIC="-//ES//DTD journal article DTD version 5.0.1//EN//XML" URI="art501.dtd" name="istex:docType"></istex:docType><istex:document><article version="5.0" xml:lang="en" docsubtype="fla"><item-info><jid>ICA</jid><aid>97059112</aid><ce:pii>S0020-1693(97)05911-2</ce:pii><ce:doi>10.1016/S0020-1693(97)05911-2</ce:doi><ce:copyright type="unknown" year="1998">Elsevier Science S.A. All rights reserved.</ce:copyright></item-info><head><ce:title>Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of <ce:italic>cis</ce:italic>, <ce:italic>trans</ce:italic>-bis(2-dimethyl-aminoethyl)-diphenyl-phosphino(dichloro)ruthenium(II)</ce:title><ce:author-group><ce:author><ce:given-name>Zijian</ce:given-name><ce:surname>Guo</ce:surname><ce:cross-ref refid="aff1"><ce:sup>a</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>Abraha</ce:given-name><ce:surname>Habtemariam</ce:surname><ce:cross-ref refid="aff1"><ce:sup>a</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>Peter J.</ce:given-name><ce:surname>Sadler</ce:surname><ce:cross-ref refid="aff1"><ce:sup>a</ce:sup></ce:cross-ref><ce:cross-ref refid="cor1"><ce:sup>*</ce:sup></ce:cross-ref><ce:e-address type="email">P.J.@ed.ac.uk</ce:e-address></ce:author><ce:author><ce:given-name>Brian R.</ce:given-name><ce:surname>James</ce:surname><ce:cross-ref refid="aff2"><ce:sup>b</ce:sup></ce:cross-ref></ce:author><ce:affiliation id="aff1"><ce:label>a</ce:label><ce:textfn>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</ce:textfn></ce:affiliation><ce:affiliation id="aff2"><ce:label>b</ce:label><ce:textfn>Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1ZI, Canada</ce:textfn></ce:affiliation><ce:correspondence id="cor1"><ce:label>*</ce:label><ce:text>Corresponding author. Tel.: +44 131 650 4729; fax: +44 131 650 6542;</ce:text></ce:correspondence></ce:author-group><ce:date-received day="3" month="4" year="1997"></ce:date-received><ce:date-revised day="22" month="5" year="1997"></ce:date-revised><ce:date-accepted day="13" month="6" year="1997"></ce:date-accepted><ce:abstract id="ab1" class="author" xml:lang="en"><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>The Ru(II) complex <ce:italic>cis</ce:italic>,<ce:italic>trans</ce:italic>-[Ru(Me<ce:inf loc="post">2</ce:inf>NCH<ce:inf loc="post">2</ce:inf>CH<ce:inf loc="post">2</ce:inf>PPh<ce:inf loc="post">2</ce:inf>-<ce:italic>P</ce:italic>,<ce:italic>N</ce:italic>)<ce:inf loc="post">2</ce:inf>Cl<ce:inf loc="post">2</ce:inf>] (<ce:bold>1</ce:bold>) has been characterized in the solid state and in solution. X-ray crystallography showed that complex <ce:bold>1</ce:bold> is monoclinic, space group <ce:italic>C</ce:italic><ce:inf loc="post">2</ce:inf>/<ce:italic>c</ce:italic>; <ce:italic>a</ce:italic> = 36.0421, <ce:italic>b</ce:italic> = 11.4866, <ce:italic>c</ce:italic> = 31.0540 Å; <ce:italic>β</ce:italic> = 104.556°. The structure refined to <ce:italic>R</ce:italic> = 0.0925 and <ce:italic>Rw</ce:italic> = 0.223. There are two independent molecules in the unit cell, with normal Ru-P bonds (2.24–2.26 Å), but the Ru-N bonds (2.37–2.42 Å) are 0.2 Å longer than typical values for Ru-N <ce:italic>trans</ce:italic> to phosphorus. The Cl-Ru-Cl bond angles of <ce:bold>1</ce:bold> are 171.78 and 173.14°. Complex <ce:bold>1</ce:bold> is stable in methylene chloride solution and cyclic voltammetry showed that it undergoes a fully reversible one-electron oxidation at 0.326 V. In methanol, however, <ce:bold>1</ce:bold> (both in air or under N<ce:inf loc="post">2</ce:inf>) undergoes a two-stage ionization/solvolysis with first order constants at 293 K: 5.40 ± 0.02 × 10<ce:sup loc="post">−4</ce:sup> s<ce:sup loc="post">−1</ce:sup> for the first step, and 3.29 ± 0.03 × 10<ce:sup loc="post">−5</ce:sup> s<ce:sup loc="post">−1</ce:sup> for the second step accompanied by a colour change from red to green. <ce:sup loc="post">1</ce:sup>H and <ce:sup loc="post">31</ce:sup>P{<ce:sup loc="post">1</ce:sup>H} NMR spectroscopic studies suggest that the solvolysis is accompanied by P,N-chelate ring-opening. These processes are inhibited by the presence of excess of lithium chloride.</ce:simple-para></ce:abstract-sec></ce:abstract><ce:keywords class="keyword" xml:lang="en"><ce:section-title>Keywords</ce:section-title><ce:keyword><ce:text>Ruthenium complexes</ce:text></ce:keyword><ce:keyword><ce:text>Aminophosphine complexes</ce:text></ce:keyword><ce:keyword><ce:text>Crystal structures</ce:text></ce:keyword><ce:keyword><ce:text>Chelate ring complexes</ce:text></ce:keyword></ce:keywords></head><tail><ce:bibliography><ce:section-title>References</ce:section-title><ce:bibliography-sec><ce:bib-reference id="bib1"><ce:label>[1]</ce:label><sb:reference><ce:label>(a)</ce:label><sb:contribution langtype="en"><sb:authors><sb:author><ce:given-name>B.K.</ce:given-name><ce:surname>Keppler</ce:surname></sb:author></sb:authors></sb:contribution><sb:host><sb:issue><sb:series><sb:title><sb:maintitle>New J. 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Rev.</sb:maintitle></sb:title><sb:volume-nr>7</sb:volume-nr></sb:series><sb:date>1971</sb:date></sb:issue><sb:pages><sb:first-page>81</sb:first-page></sb:pages></sb:host></sb:reference></ce:bib-reference></ce:bibliography-sec></ce:bibliography></tail></article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of cis , trans -bis(2-dimethyl-aminoethyl)-diphenyl-phosphino(dichloro)ruthenium(II)</title></titleInfo><titleInfo type="alternative" lang="en" contentType="CDATA"><title>Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of</title></titleInfo><name type="personal"><namePart type="given">Zijian</namePart><namePart type="family">Guo</namePart><affiliation>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Abraha</namePart><namePart type="family">Habtemariam</namePart><affiliation>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Peter J.</namePart><namePart type="family">Sadler</namePart><affiliation>Department of Chemistry, The University of Edinburgh, Edinburgh EH9 3JJ, UK</affiliation><affiliation>Corresponding author. Tel.: +44 131 650 4729; fax: +44 131 650 6542;</affiliation><affiliation>E-mail: P.J.@ed.ac.uk</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Brian R.</namePart><namePart type="family">James</namePart><affiliation>Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1ZI, Canada</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="research-article" displayLabel="Full-length article"></genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">1998</dateIssued><dateModified encoding="w3cdtf">1997-05-22</dateModified><copyrightDate encoding="w3cdtf">1998</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">Abstract: The Ru(II) complex cis,trans-[Ru(Me2NCH2CH2PPh2-P,N)2Cl2] (1) has been characterized in the solid state and in solution. X-ray crystallography showed that complex 1 is monoclinic, space group C2/c; a = 36.0421, b = 11.4866, c = 31.0540 Å; β = 104.556°. The structure refined to R = 0.0925 and Rw = 0.223. There are two independent molecules in the unit cell, with normal Ru-P bonds (2.24–2.26 Å), but the Ru-N bonds (2.37–2.42 Å) are 0.2 Å longer than typical values for Ru-N trans to phosphorus. The Cl-Ru-Cl bond angles of 1 are 171.78 and 173.14°. Complex 1 is stable in methylene chloride solution and cyclic voltammetry showed that it undergoes a fully reversible one-electron oxidation at 0.326 V. In methanol, however, 1 (both in air or under N2) undergoes a two-stage ionization/solvolysis with first order constants at 293 K: 5.40 ± 0.02 × 10−4 s−1 for the first step, and 3.29 ± 0.03 × 10−5 s−1 for the second step accompanied by a colour change from red to green. 1H and 31P{1H} NMR spectroscopic studies suggest that the solvolysis is accompanied by P,N-chelate ring-opening. These processes are inhibited by the presence of excess of lithium chloride.</abstract><subject lang="en"><genre>Keywords</genre><topic>Ruthenium complexes</topic><topic>Aminophosphine complexes</topic><topic>Crystal structures</topic><topic>Chelate ring complexes</topic></subject><relatedItem type="host"><titleInfo><title>Inorganica Chimica Acta</title></titleInfo><titleInfo type="abbreviated"><title>ICA</title></titleInfo><genre type="journal">journal</genre><originInfo><dateIssued encoding="w3cdtf">19980515</dateIssued></originInfo><identifier type="ISSN">0020-1693</identifier><identifier type="PII">S0020-1693(00)X0592-0</identifier><part><date>19980515</date><detail type="volume"><number>273</number><caption>vol.</caption></detail><detail type="issue"><number>1–2</number><caption>no.</caption></detail><extent unit="issue pages"><start>1</start><end>424</end></extent><extent unit="pages"><start>1</start><end>7</end></extent></part></relatedItem><identifier type="istex">D2884690EA5D10E7574042D63947CB0A1748D3C4</identifier><identifier type="DOI">10.1016/S0020-1693(97)05911-2</identifier><identifier type="PII">S0020-1693(97)05911-2</identifier><identifier type="ArticleID">97059112</identifier><accessCondition type="use and reproduction" contentType="copyright">©1998 Elsevier Science S.A. 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