NMR studies of some η4-diene-rhodium(I) and main group metal derivatives of funtionally substituted cyclopentadienes
Identifieur interne : 000547 ( Istex/Corpus ); précédent : 000546; suivant : 000548NMR studies of some η4-diene-rhodium(I) and main group metal derivatives of funtionally substituted cyclopentadienes
Auteurs : Michael Arthurs ; Peter Gross ; Gina Kubal ; Larysa Paniwnyk ; Eirian CurzonSource :
- Journal of Organometallic Chemistry [ 0022-328X ] ; 1988.
Abstract
The carbon-13 NMR spectra of twenty four acyclic and cyclic η4-1,3-, 1,4- and 1,5-diene-rhodium(I) complexes of type η5-C5H4XRh (η4-diene), (X =H, Cl, Ph, CO2CH3 or CHO) are described. Each diene type can be easily distinguished from the values of its 103Rh13C coupling constants and olefincarbon coordination shifts. The effects of methyl substituents on the relative chemical shifts of the acyclic η4-1,3-diene carbon atom are broadly similar to that in analogous η4-dienetricarbonyliron systems, but the metalcarbon coupling constants imply a greater degree of retrodative bonding in the case of the rhodium complexes. The largest coordination shifts are found for the β olefin carbons of the 1,4-diene complexes. The unusual metalcarbon coupling in these complexes are a reflection of the strained conformation adopted on bonding to rhodium, and do not suggest conjugative interaction between the two alkene functions. The spectra of the 1,5-diene complexes show the expected trend resulting from a reduction in strain energy relative to that for the previous case. The spectra of the η5-cyclopentadienyl groups in these complexes as discussed in terms of a small contribution from either an η3-allyl-η2-ene or a η4-diolefin-η1-alkyl rotamer to the metalring bonding scheme; the rotamer type is governed by the cyclopentadienyl ring substituent and counter diene ligand. Several functionally-substituted cyclopentadienide salts have been examined by variable temperature hydrogen-1 and carbon-13 NMR spectroscopy. The fluxional behaviour of Tl1(C5H4NO2 and K(C5H4CHO) demonstrate how the Lewis acid character of the metal ion and the electron-accepting nature of the ring substituent control the structural preference for a form in which the substituent is either co-planar or orthogonal with respect to the cyclopentadienide group. Two dimensional 1H13C NMR spectra and simulation techniques peritted unambiguous assignment of ring nuclei. The chemical ionisation and fast atom bombardment mass spectra of several of the thallium(I) complexes reveal considerable association in the vapour state.
Url:
DOI: 10.1016/0022-328X(89)87329-2
Links to Exploration step
ISTEX:BFE6DD2799E321DADCA8B34408FC0A76875F7CB2Le document en format XML
<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title>NMR studies of some η4-diene-rhodium(I) and main group metal derivatives of funtionally substituted cyclopentadienes</title><author><name sortKey="Arthurs, Michael" sort="Arthurs, Michael" uniqKey="Arthurs M" first="Michael" last="Arthurs">Michael Arthurs</name><affiliation><mods:affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</mods:affiliation></affiliation></author><author><name sortKey="Gross, Peter" sort="Gross, Peter" uniqKey="Gross P" first="Peter" last="Gross">Peter Gross</name><affiliation><mods:affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</mods:affiliation></affiliation></author><author><name sortKey="Kubal, Gina" sort="Kubal, Gina" uniqKey="Kubal G" first="Gina" last="Kubal">Gina Kubal</name><affiliation><mods:affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</mods:affiliation></affiliation></author><author><name sortKey="Paniwnyk, Larysa" sort="Paniwnyk, Larysa" uniqKey="Paniwnyk L" first="Larysa" last="Paniwnyk">Larysa Paniwnyk</name><affiliation><mods:affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</mods:affiliation></affiliation></author><author><name sortKey="Curzon, Eirian" sort="Curzon, Eirian" uniqKey="Curzon E" first="Eirian" last="Curzon">Eirian Curzon</name><affiliation><mods:affiliation>Bruker Spectrospin Ltd, Banner Lane, Coventry CV4 9GH Great Britain</mods:affiliation></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:BFE6DD2799E321DADCA8B34408FC0A76875F7CB2</idno><date when="1989" year="1989">1989</date><idno type="doi">10.1016/0022-328X(89)87329-2</idno><idno type="url">https://api.istex.fr/document/BFE6DD2799E321DADCA8B34408FC0A76875F7CB2/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">000547</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a">NMR studies of some η4-diene-rhodium(I) and main group metal derivatives of funtionally substituted cyclopentadienes</title><author><name sortKey="Arthurs, Michael" sort="Arthurs, Michael" uniqKey="Arthurs M" first="Michael" last="Arthurs">Michael Arthurs</name><affiliation><mods:affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</mods:affiliation></affiliation></author><author><name sortKey="Gross, Peter" sort="Gross, Peter" uniqKey="Gross P" first="Peter" last="Gross">Peter Gross</name><affiliation><mods:affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</mods:affiliation></affiliation></author><author><name sortKey="Kubal, Gina" sort="Kubal, Gina" uniqKey="Kubal G" first="Gina" last="Kubal">Gina Kubal</name><affiliation><mods:affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</mods:affiliation></affiliation></author><author><name sortKey="Paniwnyk, Larysa" sort="Paniwnyk, Larysa" uniqKey="Paniwnyk L" first="Larysa" last="Paniwnyk">Larysa Paniwnyk</name><affiliation><mods:affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</mods:affiliation></affiliation></author><author><name sortKey="Curzon, Eirian" sort="Curzon, Eirian" uniqKey="Curzon E" first="Eirian" last="Curzon">Eirian Curzon</name><affiliation><mods:affiliation>Bruker Spectrospin Ltd, Banner Lane, Coventry CV4 9GH Great Britain</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Journal of Organometallic Chemistry</title><title level="j" type="abbrev">JOM</title><idno type="ISSN">0022-328X</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1988">1988</date><biblScope unit="volume">366</biblScope><biblScope unit="issue">1–2</biblScope><biblScope unit="page" from="223">223</biblScope><biblScope unit="page" to="243">243</biblScope></imprint><idno type="ISSN">0022-328X</idno></series><idno type="istex">BFE6DD2799E321DADCA8B34408FC0A76875F7CB2</idno><idno type="DOI">10.1016/0022-328X(89)87329-2</idno><idno type="PII">0022-328X(89)87329-2</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0022-328X</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The carbon-13 NMR spectra of twenty four acyclic and cyclic η4-1,3-, 1,4- and 1,5-diene-rhodium(I) complexes of type η5-C5H4XRh (η4-diene), (X =H, Cl, Ph, CO2CH3 or CHO) are described. Each diene type can be easily distinguished from the values of its 103Rh13C coupling constants and olefincarbon coordination shifts. The effects of methyl substituents on the relative chemical shifts of the acyclic η4-1,3-diene carbon atom are broadly similar to that in analogous η4-dienetricarbonyliron systems, but the metalcarbon coupling constants imply a greater degree of retrodative bonding in the case of the rhodium complexes. The largest coordination shifts are found for the β olefin carbons of the 1,4-diene complexes. The unusual metalcarbon coupling in these complexes are a reflection of the strained conformation adopted on bonding to rhodium, and do not suggest conjugative interaction between the two alkene functions. The spectra of the 1,5-diene complexes show the expected trend resulting from a reduction in strain energy relative to that for the previous case. The spectra of the η5-cyclopentadienyl groups in these complexes as discussed in terms of a small contribution from either an η3-allyl-η2-ene or a η4-diolefin-η1-alkyl rotamer to the metalring bonding scheme; the rotamer type is governed by the cyclopentadienyl ring substituent and counter diene ligand. Several functionally-substituted cyclopentadienide salts have been examined by variable temperature hydrogen-1 and carbon-13 NMR spectroscopy. The fluxional behaviour of Tl1(C5H4NO2 and K(C5H4CHO) demonstrate how the Lewis acid character of the metal ion and the electron-accepting nature of the ring substituent control the structural preference for a form in which the substituent is either co-planar or orthogonal with respect to the cyclopentadienide group. Two dimensional 1H13C NMR spectra and simulation techniques peritted unambiguous assignment of ring nuclei. The chemical ionisation and fast atom bombardment mass spectra of several of the thallium(I) complexes reveal considerable association in the vapour state.</div></front></TEI><istex><corpusName>elsevier</corpusName><author><json:item><name>Michael Arthurs</name><affiliations><json:string>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</json:string></affiliations></json:item><json:item><name>Peter Gross</name><affiliations><json:string>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</json:string></affiliations></json:item><json:item><name>Gina Kubal</name><affiliations><json:string>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</json:string></affiliations></json:item><json:item><name>Larysa Paniwnyk</name><affiliations><json:string>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</json:string></affiliations></json:item><json:item><name>Eirian Curzon</name><affiliations><json:string>Bruker Spectrospin Ltd, Banner Lane, Coventry CV4 9GH Great Britain</json:string></affiliations></json:item></author><language><json:string>eng</json:string></language><abstract>The carbon-13 NMR spectra of twenty four acyclic and cyclic η4-1,3-, 1,4- and 1,5-diene-rhodium(I) complexes of type η5-C5H4XRh (η4-diene), (X =H, Cl, Ph, CO2CH3 or CHO) are described. Each diene type can be easily distinguished from the values of its 103Rh13C coupling constants and olefincarbon coordination shifts. The effects of methyl substituents on the relative chemical shifts of the acyclic η4-1,3-diene carbon atom are broadly similar to that in analogous η4-dienetricarbonyliron systems, but the metalcarbon coupling constants imply a greater degree of retrodative bonding in the case of the rhodium complexes. The largest coordination shifts are found for the β olefin carbons of the 1,4-diene complexes. The unusual metalcarbon coupling in these complexes are a reflection of the strained conformation adopted on bonding to rhodium, and do not suggest conjugative interaction between the two alkene functions. The spectra of the 1,5-diene complexes show the expected trend resulting from a reduction in strain energy relative to that for the previous case. The spectra of the η5-cyclopentadienyl groups in these complexes as discussed in terms of a small contribution from either an η3-allyl-η2-ene or a η4-diolefin-η1-alkyl rotamer to the metalring bonding scheme; the rotamer type is governed by the cyclopentadienyl ring substituent and counter diene ligand. Several functionally-substituted cyclopentadienide salts have been examined by variable temperature hydrogen-1 and carbon-13 NMR spectroscopy. The fluxional behaviour of Tl1(C5H4NO2 and K(C5H4CHO) demonstrate how the Lewis acid character of the metal ion and the electron-accepting nature of the ring substituent control the structural preference for a form in which the substituent is either co-planar or orthogonal with respect to the cyclopentadienide group. Two dimensional 1H13C NMR spectra and simulation techniques peritted unambiguous assignment of ring nuclei. The chemical ionisation and fast atom bombardment mass spectra of several of the thallium(I) complexes reveal considerable association in the vapour state.</abstract><qualityIndicators><score>8</score><pdfVersion>1.2</pdfVersion><pdfPageSize>510 x 700 pts</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>0</keywordCount><abstractCharCount>2106</abstractCharCount><pdfWordCount>6204</pdfWordCount><pdfCharCount>41427</pdfCharCount><pdfPageCount>21</pdfPageCount><abstractWordCount>302</abstractWordCount></qualityIndicators><title>NMR studies of some η4-diene-rhodium(I) and main group metal derivatives of funtionally substituted cyclopentadienes</title><pii><json:string>0022-328X(89)87329-2</json:string></pii><genre><json:string>research-article</json:string></genre><host><volume>366</volume><pii><json:string>S0022-328X(00)X1045-5</json:string></pii><pages><last>243</last><first>223</first></pages><issn><json:string>0022-328X</json:string></issn><issue>1–2</issue><genre><json:string>Journal</json:string></genre><language><json:string>unknown</json:string></language><title>Journal of Organometallic Chemistry</title><publicationDate>1989</publicationDate></host><categories><wos><json:string>CHEMISTRY, INORGANIC & NUCLEAR</json:string><json:string>CHEMISTRY, ORGANIC</json:string></wos></categories><publicationDate>1988</publicationDate><copyrightDate>1989</copyrightDate><doi><json:string>10.1016/0022-328X(89)87329-2</json:string></doi><id>BFE6DD2799E321DADCA8B34408FC0A76875F7CB2</id><score>1</score><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/BFE6DD2799E321DADCA8B34408FC0A76875F7CB2/fulltext/pdf</uri></json:item><json:item><original>true</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/BFE6DD2799E321DADCA8B34408FC0A76875F7CB2/fulltext/txt</uri></json:item><json:item><original>false</original><mimetype>application/zip</mimetype><extension>zip</extension><uri>https://api.istex.fr/document/BFE6DD2799E321DADCA8B34408FC0A76875F7CB2/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/BFE6DD2799E321DADCA8B34408FC0A76875F7CB2/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a">NMR studies of some η4-diene-rhodium(I) and main group metal derivatives of funtionally substituted cyclopentadienes</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>ELSEVIER</publisher><availability><p>ELSEVIER</p></availability><date>1989</date></publicationStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a">NMR studies of some η4-diene-rhodium(I) and main group metal derivatives of funtionally substituted cyclopentadienes</title><author><persName><forename type="first">Michael</forename><surname>Arthurs</surname></persName><affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</affiliation></author><author><persName><forename type="first">Peter</forename><surname>Gross</surname></persName><affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</affiliation></author><author><persName><forename type="first">Gina</forename><surname>Kubal</surname></persName><affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</affiliation></author><author><persName><forename type="first">Larysa</forename><surname>Paniwnyk</surname></persName><affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</affiliation></author><author><persName><forename type="first">Eirian</forename><surname>Curzon</surname></persName><affiliation>Bruker Spectrospin Ltd, Banner Lane, Coventry CV4 9GH Great Britain</affiliation></author></analytic><monogr><title level="j">Journal of Organometallic Chemistry</title><title level="j" type="abbrev">JOM</title><idno type="pISSN">0022-328X</idno><idno type="PII">S0022-328X(00)X1045-5</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1988"></date><biblScope unit="volume">366</biblScope><biblScope unit="issue">1–2</biblScope><biblScope unit="page" from="223">223</biblScope><biblScope unit="page" to="243">243</biblScope></imprint></monogr><idno type="istex">BFE6DD2799E321DADCA8B34408FC0A76875F7CB2</idno><idno type="DOI">10.1016/0022-328X(89)87329-2</idno><idno type="PII">0022-328X(89)87329-2</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>1989</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>The carbon-13 NMR spectra of twenty four acyclic and cyclic η4-1,3-, 1,4- and 1,5-diene-rhodium(I) complexes of type η5-C5H4XRh (η4-diene), (X =H, Cl, Ph, CO2CH3 or CHO) are described. Each diene type can be easily distinguished from the values of its 103Rh13C coupling constants and olefincarbon coordination shifts. The effects of methyl substituents on the relative chemical shifts of the acyclic η4-1,3-diene carbon atom are broadly similar to that in analogous η4-dienetricarbonyliron systems, but the metalcarbon coupling constants imply a greater degree of retrodative bonding in the case of the rhodium complexes. The largest coordination shifts are found for the β olefin carbons of the 1,4-diene complexes. The unusual metalcarbon coupling in these complexes are a reflection of the strained conformation adopted on bonding to rhodium, and do not suggest conjugative interaction between the two alkene functions. The spectra of the 1,5-diene complexes show the expected trend resulting from a reduction in strain energy relative to that for the previous case. The spectra of the η5-cyclopentadienyl groups in these complexes as discussed in terms of a small contribution from either an η3-allyl-η2-ene or a η4-diolefin-η1-alkyl rotamer to the metalring bonding scheme; the rotamer type is governed by the cyclopentadienyl ring substituent and counter diene ligand. Several functionally-substituted cyclopentadienide salts have been examined by variable temperature hydrogen-1 and carbon-13 NMR spectroscopy. The fluxional behaviour of Tl1(C5H4NO2 and K(C5H4CHO) demonstrate how the Lewis acid character of the metal ion and the electron-accepting nature of the ring substituent control the structural preference for a form in which the substituent is either co-planar or orthogonal with respect to the cyclopentadienide group. Two dimensional 1H13C NMR spectra and simulation techniques peritted unambiguous assignment of ring nuclei. The chemical ionisation and fast atom bombardment mass spectra of several of the thallium(I) complexes reveal considerable association in the vapour state.</p></abstract></profileDesc><revisionDesc><change when="1988-09-26">Received</change><change when="1988">Published</change></revisionDesc></teiHeader></istex:fulltextTEI></fulltext><metadata><istex:metadataXml wicri:clean="Elsevier, elements deleted: tail"><istex:xmlDeclaration>version="1.0" encoding="utf-8"</istex:xmlDeclaration><istex:docType PUBLIC="-//ES//DTD journal article DTD version 4.5.2//EN//XML" URI="art452.dtd" name="istex:docType"></istex:docType><istex:document><converted-article version="4.5.2" docsubtype="fla"><item-info><jid>JOM</jid><aid>89873292</aid><ce:pii>0022-328X(89)87329-2</ce:pii><ce:doi>10.1016/0022-328X(89)87329-2</ce:doi><ce:copyright type="unknown" year="1989"></ce:copyright></item-info><head><ce:title>NMR studies of some η<ce:sup>4</ce:sup>-diene-rhodium(I) and main group metal derivatives of funtionally substituted cyclopentadienes</ce:title><ce:author-group><ce:author><ce:given-name>Michael</ce:given-name><ce:surname>Arthurs</ce:surname><ce:ranking><ce:sup>∗</ce:sup></ce:ranking></ce:author><ce:author><ce:given-name>Peter</ce:given-name><ce:surname>Gross</ce:surname></ce:author><ce:author><ce:given-name>Gina</ce:given-name><ce:surname>Kubal</ce:surname></ce:author><ce:author><ce:given-name>Larysa</ce:given-name><ce:surname>Paniwnyk</ce:surname></ce:author><ce:affiliation><ce:textfn>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</ce:textfn></ce:affiliation></ce:author-group><ce:author-group><ce:author><ce:given-name>Eirian</ce:given-name><ce:surname>Curzon</ce:surname></ce:author><ce:affiliation><ce:textfn>Bruker Spectrospin Ltd, Banner Lane, Coventry CV4 9GH Great Britain</ce:textfn></ce:affiliation></ce:author-group><ce:date-received day="26" month="9" year="1988"></ce:date-received><ce:abstract><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>The carbon-13 NMR spectra of twenty four acyclic and cyclic η<ce:sup>4</ce:sup>-1,3-, 1,4- and 1,5-diene-rhodium(I) complexes of type η<ce:sup>5</ce:sup>-C<ce:inf>5</ce:inf>H<ce:inf>4</ce:inf>XRh (η<ce:sup>4</ce:sup>-diene), (X =H, Cl, Ph, CO<ce:inf>2</ce:inf>CH<ce:inf>3</ce:inf> or CHO) are described. Each diene type can be easily distinguished from the values of its <ce:sup loc="pre">103</ce:sup>Rh<ce:sup>13</ce:sup>C coupling constants and olefincarbon coordination shifts. The effects of methyl substituents on the relative chemical shifts of the acyclic η<ce:sup>4</ce:sup>-1,3-diene carbon atom are broadly similar to that in analogous η<ce:sup>4</ce:sup>-dienetricarbonyliron systems, but the metalcarbon coupling constants imply a greater degree of retrodative bonding in the case of the rhodium complexes. The largest coordination shifts are found for the β olefin carbons of the 1,4-diene complexes. The unusual metalcarbon coupling in these complexes are a reflection of the strained conformation adopted on bonding to rhodium, and do not suggest conjugative interaction between the two alkene functions. The spectra of the 1,5-diene complexes show the expected trend resulting from a reduction in strain energy relative to that for the previous case. The spectra of the η<ce:sup>5</ce:sup>-cyclopentadienyl groups in these complexes as discussed in terms of a small contribution from either an η<ce:sup>3</ce:sup>-allyl-η<ce:sup>2</ce:sup>-ene or a η<ce:sup>4</ce:sup>-diolefin-η<ce:sup>1</ce:sup>-alkyl rotamer to the metalring bonding scheme; the rotamer type is governed by the cyclopentadienyl ring substituent and counter diene ligand. Several functionally-substituted cyclopentadienide salts have been examined by variable temperature hydrogen-1 and carbon-13 NMR spectroscopy. The fluxional behaviour of Tl<ce:sup>1</ce:sup>(C<ce:inf>5</ce:inf>H<ce:inf>4</ce:inf>NO<ce:inf>2</ce:inf> and K(C<ce:inf>5</ce:inf>H<ce:inf>4</ce:inf>CHO) demonstrate how the Lewis acid character of the metal ion and the electron-accepting nature of the ring substituent control the structural preference for a form in which the substituent is either co-planar or orthogonal with respect to the cyclopentadienide group. Two dimensional <ce:sup loc="pre">1</ce:sup>H<ce:sup>13</ce:sup>C NMR spectra and simulation techniques peritted unambiguous assignment of ring nuclei. The chemical ionisation and fast atom bombardment mass spectra of several of the thallium(I) complexes reveal considerable association in the vapour state.</ce:simple-para></ce:abstract-sec></ce:abstract></head></converted-article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo><title>NMR studies of some η4-diene-rhodium(I) and main group metal derivatives of funtionally substituted cyclopentadienes</title></titleInfo><titleInfo type="alternative" contentType="CDATA"><title>NMR studies of some η</title></titleInfo><name type="personal"><namePart type="given">Michael</namePart><namePart type="family">Arthurs</namePart><affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Peter</namePart><namePart type="family">Gross</namePart><affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Gina</namePart><namePart type="family">Kubal</namePart><affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Larysa</namePart><namePart type="family">Paniwnyk</namePart><affiliation>School of Applied Chemistry, Coventry Polytechnic, Priory Street, Coventry, CV1 5FB Great Britain</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Eirian</namePart><namePart type="family">Curzon</namePart><affiliation>Bruker Spectrospin Ltd, Banner Lane, Coventry CV4 9GH Great Britain</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">1988</dateIssued><dateCaptured encoding="w3cdtf">1988-09-26</dateCaptured><copyrightDate encoding="w3cdtf">1989</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">The carbon-13 NMR spectra of twenty four acyclic and cyclic η4-1,3-, 1,4- and 1,5-diene-rhodium(I) complexes of type η5-C5H4XRh (η4-diene), (X =H, Cl, Ph, CO2CH3 or CHO) are described. Each diene type can be easily distinguished from the values of its 103Rh13C coupling constants and olefincarbon coordination shifts. The effects of methyl substituents on the relative chemical shifts of the acyclic η4-1,3-diene carbon atom are broadly similar to that in analogous η4-dienetricarbonyliron systems, but the metalcarbon coupling constants imply a greater degree of retrodative bonding in the case of the rhodium complexes. The largest coordination shifts are found for the β olefin carbons of the 1,4-diene complexes. The unusual metalcarbon coupling in these complexes are a reflection of the strained conformation adopted on bonding to rhodium, and do not suggest conjugative interaction between the two alkene functions. The spectra of the 1,5-diene complexes show the expected trend resulting from a reduction in strain energy relative to that for the previous case. The spectra of the η5-cyclopentadienyl groups in these complexes as discussed in terms of a small contribution from either an η3-allyl-η2-ene or a η4-diolefin-η1-alkyl rotamer to the metalring bonding scheme; the rotamer type is governed by the cyclopentadienyl ring substituent and counter diene ligand. Several functionally-substituted cyclopentadienide salts have been examined by variable temperature hydrogen-1 and carbon-13 NMR spectroscopy. The fluxional behaviour of Tl1(C5H4NO2 and K(C5H4CHO) demonstrate how the Lewis acid character of the metal ion and the electron-accepting nature of the ring substituent control the structural preference for a form in which the substituent is either co-planar or orthogonal with respect to the cyclopentadienide group. Two dimensional 1H13C NMR spectra and simulation techniques peritted unambiguous assignment of ring nuclei. The chemical ionisation and fast atom bombardment mass spectra of several of the thallium(I) complexes reveal considerable association in the vapour state.</abstract><relatedItem type="host"><titleInfo><title>Journal of Organometallic Chemistry</title></titleInfo><titleInfo type="abbreviated"><title>JOM</title></titleInfo><genre type="Journal">journal</genre><originInfo><dateIssued encoding="w3cdtf">19890425</dateIssued></originInfo><identifier type="ISSN">0022-328X</identifier><identifier type="PII">S0022-328X(00)X1045-5</identifier><part><date>19890425</date><detail type="volume"><number>366</number><caption>vol.</caption></detail><detail type="issue"><number>1–2</number><caption>no.</caption></detail><extent unit="issue pages"><start>C1</start><end>C14</end></extent><extent unit="issue pages"><start>1</start><end>280</end></extent><extent unit="pages"><start>223</start><end>243</end></extent></part></relatedItem><identifier type="istex">BFE6DD2799E321DADCA8B34408FC0A76875F7CB2</identifier><identifier type="DOI">10.1016/0022-328X(89)87329-2</identifier><identifier type="PII">0022-328X(89)87329-2</identifier><recordInfo><recordContentSource>ELSEVIER</recordContentSource></recordInfo></mods></metadata><enrichments><istex:catWosTEI uri="https://api.istex.fr/document/BFE6DD2799E321DADCA8B34408FC0A76875F7CB2/enrichments/catWos"><teiHeader><profileDesc><textClass><classCode scheme="WOS">CHEMISTRY, INORGANIC & NUCLEAR</classCode><classCode scheme="WOS">CHEMISTRY, ORGANIC</classCode></textClass></profileDesc></teiHeader></istex:catWosTEI></enrichments><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Ticri/CIDE/explor/HapticV1/Data/Istex/Corpus
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 000547 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Istex/Corpus/biblio.hfd -nk 000547 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= Ticri/CIDE
|area= HapticV1
|flux= Istex
|étape= Corpus
|type= RBID
|clé= ISTEX:BFE6DD2799E321DADCA8B34408FC0A76875F7CB2
|texte= NMR studies of some η4-diene-rhodium(I) and main group metal derivatives of funtionally substituted cyclopentadienes
}}
| This area was generated with Dilib version V0.6.23. |  |