Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d -electron count
Identifieur interne : 003367 ( Istex/Corpus ); précédent : 003366; suivant : 003368Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d -electron count
Auteurs : Steve A. Westcott ; Ashok K. Kakkar ; Graham Stringer ; Nicholas J. Taylor ; Todd B. MarderSource :
- Journal of Organometallic Chemistry [ 0022-328X ] ; 1990.
Abstract
The crystal and molecular structures of [(η-C9H7)2M] (M = Fe, 1; Co, 2; Ni, 3) and [(η-C9Me7)2Fe], 4, are reported, along with a discussion of the correlation between hapticity and the 13C chemical shift of the indenyl ring-junction carbons (C(3a), C(7a)). Single crystals of both 1 and 2 undergo non-destructive and reversible phase changes upon cooling below ca. 240–245 K. The room-temperature structures are disordered; however, the low temperature ones (150 K) are essentially ordered. Crystals of 3 do not display this behavior on cooling to 150 K, and residual anisotropy in certain carbon atoms is ascribed to a minor twinning problem. Crystals of 4 were only examined at ambient temperature, where an ordered structure was obtained. In contrast to the analogous Cp2M series (Cp = η5-C5H5; M = Fe, Co, Ni), which display a gradual symmetric increase in MC distances in the order Fe < Co < Ni, the distortions in the indenyl series are of a fundamentally different nature. Thus, there is a gradual increase in the degree of slip-fold distortion from η5- toward η3-coordination which involves (a) slippage of the metal away from C(3a),C(7a), and (b) folding of the ring system (particularly at C(1),C(3)), in the order Fe < Co < Ni. The slip values (Δ = avg d(MC(3a),C(7a)) − avg d(MC(1),C(3)) are 0.043(4), 0.124(4), 0.418(6), and 0.030(4) Å for 1–4, respectively. For a “true η5”-complex, Δ should be ca. 0 Å, whereas values of ca. 0.69–0.79 Å have been reported for “true η3-”indenyl complexes such as [(η3-C9H7)Ir(PMe2Ph)3]. Therefore, complexes 1 and 4 are clearly η5, as predicted on the basis of the 18-electron rule, whereas 2 and 3 display increasing degrees of distortion in both rings to avoid 19- and 20-electron counts, respectively. The two indenyl rings in 3 are half-way between η5- and η3-coordination modes. Crystal data for 1 at 295 K are: monoclinic, P21 n, a 8.030(2), b 7.806(2), c 10.779(2) Å, β 107.39(1)°, V 648.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, Cc, a 16.021(4), b 15.510(5), c 11.187(3) Å, β 115.53(2)°, V 2509(1) Å3, Z = 8, R = 0.0306, Rw = 0.0332. For 2 at 295 K: monoclinic, P21 n, a 8.027(2), b 7.838(2), c 10.936(3) Å, β 107.57(2)°, V 655.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, P21 c, a 11.258(3), b 7.824(3), c 15.256(6) Å, β 108.07(2)°, V 1277.7(7) Å3, Z = 4, R = 0.0397, Rw = 0.0447. For 3, at 150 K: monoclinic, P21 n, a 6.063(1), b 20.056(3), c 10.703(2) Å, β 94.27(1)°, V 1297.9(3) Å3, Z = 4, R = 0.0413, Rw = 0.0493. For 4, at 295 K: orthorhombic, Pbcn, a 14.211(2), b 9.284(2), c 19.289(4) Å, V 2544.8(8) Å3, Z = 4, R = 0.0410, Rw = 0.0421.
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DOI: 10.1016/0022-328X(90)87268-I
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<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title>Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d -electron count</title><author><name sortKey="Westcott, Steve A" sort="Westcott, Steve A" uniqKey="Westcott S" first="Steve A." last="Westcott">Steve A. Westcott</name><affiliation><mods:affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</mods:affiliation></affiliation></author><author><name sortKey="Kakkar, Ashok K" sort="Kakkar, Ashok K" uniqKey="Kakkar A" first="Ashok K." last="Kakkar">Ashok K. Kakkar</name><affiliation><mods:affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</mods:affiliation></affiliation></author><author><name sortKey="Stringer, Graham" sort="Stringer, Graham" uniqKey="Stringer G" first="Graham" last="Stringer">Graham Stringer</name><affiliation><mods:affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</mods:affiliation></affiliation></author><author><name sortKey="Taylor, Nicholas J" sort="Taylor, Nicholas J" uniqKey="Taylor N" first="Nicholas J." last="Taylor">Nicholas J. Taylor</name><affiliation><mods:affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</mods:affiliation></affiliation></author><author><name sortKey="Marder, Todd B" sort="Marder, Todd B" uniqKey="Marder T" first="Todd B." last="Marder">Todd B. Marder</name><affiliation><mods:affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</mods:affiliation></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:E09722F8883EFAAA12C3C0B2457E7A345AC6AF63</idno><date when="1990" year="1990">1990</date><idno type="doi">10.1016/0022-328X(90)87268-I</idno><idno type="url">https://api.istex.fr/document/E09722F8883EFAAA12C3C0B2457E7A345AC6AF63/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">003367</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a">Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d -electron count</title><author><name sortKey="Westcott, Steve A" sort="Westcott, Steve A" uniqKey="Westcott S" first="Steve A." last="Westcott">Steve A. Westcott</name><affiliation><mods:affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</mods:affiliation></affiliation></author><author><name sortKey="Kakkar, Ashok K" sort="Kakkar, Ashok K" uniqKey="Kakkar A" first="Ashok K." last="Kakkar">Ashok K. Kakkar</name><affiliation><mods:affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</mods:affiliation></affiliation></author><author><name sortKey="Stringer, Graham" sort="Stringer, Graham" uniqKey="Stringer G" first="Graham" last="Stringer">Graham Stringer</name><affiliation><mods:affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</mods:affiliation></affiliation></author><author><name sortKey="Taylor, Nicholas J" sort="Taylor, Nicholas J" uniqKey="Taylor N" first="Nicholas J." last="Taylor">Nicholas J. Taylor</name><affiliation><mods:affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</mods:affiliation></affiliation></author><author><name sortKey="Marder, Todd B" sort="Marder, Todd B" uniqKey="Marder T" first="Todd B." last="Marder">Todd B. Marder</name><affiliation><mods:affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</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="1990">1990</date><biblScope unit="volume">394</biblScope><biblScope unit="issue">1–3</biblScope><biblScope unit="page" from="777">777</biblScope><biblScope unit="page" to="794">794</biblScope></imprint><idno type="ISSN">0022-328X</idno></series><idno type="istex">E09722F8883EFAAA12C3C0B2457E7A345AC6AF63</idno><idno type="DOI">10.1016/0022-328X(90)87268-I</idno><idno type="PII">0022-328X(90)87268-I</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 crystal and molecular structures of [(η-C9H7)2M] (M = Fe, 1; Co, 2; Ni, 3) and [(η-C9Me7)2Fe], 4, are reported, along with a discussion of the correlation between hapticity and the 13C chemical shift of the indenyl ring-junction carbons (C(3a), C(7a)). Single crystals of both 1 and 2 undergo non-destructive and reversible phase changes upon cooling below ca. 240–245 K. The room-temperature structures are disordered; however, the low temperature ones (150 K) are essentially ordered. Crystals of 3 do not display this behavior on cooling to 150 K, and residual anisotropy in certain carbon atoms is ascribed to a minor twinning problem. Crystals of 4 were only examined at ambient temperature, where an ordered structure was obtained. In contrast to the analogous Cp2M series (Cp = η5-C5H5; M = Fe, Co, Ni), which display a gradual symmetric increase in MC distances in the order Fe < Co < Ni, the distortions in the indenyl series are of a fundamentally different nature. Thus, there is a gradual increase in the degree of slip-fold distortion from η5- toward η3-coordination which involves (a) slippage of the metal away from C(3a),C(7a), and (b) folding of the ring system (particularly at C(1),C(3)), in the order Fe < Co < Ni. The slip values (Δ = avg d(MC(3a),C(7a)) − avg d(MC(1),C(3)) are 0.043(4), 0.124(4), 0.418(6), and 0.030(4) Å for 1–4, respectively. For a “true η5”-complex, Δ should be ca. 0 Å, whereas values of ca. 0.69–0.79 Å have been reported for “true η3-”indenyl complexes such as [(η3-C9H7)Ir(PMe2Ph)3]. Therefore, complexes 1 and 4 are clearly η5, as predicted on the basis of the 18-electron rule, whereas 2 and 3 display increasing degrees of distortion in both rings to avoid 19- and 20-electron counts, respectively. The two indenyl rings in 3 are half-way between η5- and η3-coordination modes. Crystal data for 1 at 295 K are: monoclinic, P21 n, a 8.030(2), b 7.806(2), c 10.779(2) Å, β 107.39(1)°, V 648.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, Cc, a 16.021(4), b 15.510(5), c 11.187(3) Å, β 115.53(2)°, V 2509(1) Å3, Z = 8, R = 0.0306, Rw = 0.0332. For 2 at 295 K: monoclinic, P21 n, a 8.027(2), b 7.838(2), c 10.936(3) Å, β 107.57(2)°, V 655.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, P21 c, a 11.258(3), b 7.824(3), c 15.256(6) Å, β 108.07(2)°, V 1277.7(7) Å3, Z = 4, R = 0.0397, Rw = 0.0447. For 3, at 150 K: monoclinic, P21 n, a 6.063(1), b 20.056(3), c 10.703(2) Å, β 94.27(1)°, V 1297.9(3) Å3, Z = 4, R = 0.0413, Rw = 0.0493. For 4, at 295 K: orthorhombic, Pbcn, a 14.211(2), b 9.284(2), c 19.289(4) Å, V 2544.8(8) Å3, Z = 4, R = 0.0410, Rw = 0.0421.</div></front></TEI><istex><corpusName>elsevier</corpusName><author><json:item><name>Steve A. Westcott</name><affiliations><json:string>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</json:string></affiliations></json:item><json:item><name>Ashok K. Kakkar</name><affiliations><json:string>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</json:string></affiliations></json:item><json:item><name>Graham Stringer</name><affiliations><json:string>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</json:string></affiliations></json:item><json:item><name>Nicholas J. Taylor</name><affiliations><json:string>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</json:string></affiliations></json:item><json:item><name>Todd B. Marder</name><affiliations><json:string>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</json:string></affiliations></json:item></author><language><json:string>eng</json:string></language><abstract>The crystal and molecular structures of [(η-C9H7)2M] (M = Fe, 1; Co, 2; Ni, 3) and [(η-C9Me7)2Fe], 4, are reported, along with a discussion of the correlation between hapticity and the 13C chemical shift of the indenyl ring-junction carbons (C(3a), C(7a)). Single crystals of both 1 and 2 undergo non-destructive and reversible phase changes upon cooling below ca. 240–245 K. The room-temperature structures are disordered; however, the low temperature ones (150 K) are essentially ordered. Crystals of 3 do not display this behavior on cooling to 150 K, and residual anisotropy in certain carbon atoms is ascribed to a minor twinning problem. Crystals of 4 were only examined at ambient temperature, where an ordered structure was obtained. In contrast to the analogous Cp2M series (Cp = η5-C5H5; M = Fe, Co, Ni), which display a gradual symmetric increase in MC distances in the order Fe > Co > Ni, the distortions in the indenyl series are of a fundamentally different nature. Thus, there is a gradual increase in the degree of slip-fold distortion from η5- toward η3-coordination which involves (a) slippage of the metal away from C(3a),C(7a), and (b) folding of the ring system (particularly at C(1),C(3)), in the order Fe > Co > Ni. The slip values (Δ = avg d(MC(3a),C(7a)) − avg d(MC(1),C(3)) are 0.043(4), 0.124(4), 0.418(6), and 0.030(4) Å for 1–4, respectively. For a “true η5”-complex, Δ should be ca. 0 Å, whereas values of ca. 0.69–0.79 Å have been reported for “true η3-”indenyl complexes such as [(η3-C9H7)Ir(PMe2Ph)3]. Therefore, complexes 1 and 4 are clearly η5, as predicted on the basis of the 18-electron rule, whereas 2 and 3 display increasing degrees of distortion in both rings to avoid 19- and 20-electron counts, respectively. The two indenyl rings in 3 are half-way between η5- and η3-coordination modes. Crystal data for 1 at 295 K are: monoclinic, P21 n, a 8.030(2), b 7.806(2), c 10.779(2) Å, β 107.39(1)°, V 648.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, Cc, a 16.021(4), b 15.510(5), c 11.187(3) Å, β 115.53(2)°, V 2509(1) Å3, Z = 8, R = 0.0306, Rw = 0.0332. For 2 at 295 K: monoclinic, P21 n, a 8.027(2), b 7.838(2), c 10.936(3) Å, β 107.57(2)°, V 655.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, P21 c, a 11.258(3), b 7.824(3), c 15.256(6) Å, β 108.07(2)°, V 1277.7(7) Å3, Z = 4, R = 0.0397, Rw = 0.0447. For 3, at 150 K: monoclinic, P21 n, a 6.063(1), b 20.056(3), c 10.703(2) Å, β 94.27(1)°, V 1297.9(3) Å3, Z = 4, R = 0.0413, Rw = 0.0493. For 4, at 295 K: orthorhombic, Pbcn, a 14.211(2), b 9.284(2), c 19.289(4) Å, V 2544.8(8) Å3, Z = 4, R = 0.0410, Rw = 0.0421.</abstract><qualityIndicators><score>8</score><pdfVersion>1.2</pdfVersion><pdfPageSize>510 x 700 pts</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>0</keywordCount><abstractCharCount>2637</abstractCharCount><pdfWordCount>5661</pdfWordCount><pdfCharCount>36173</pdfCharCount><pdfPageCount>18</pdfPageCount><abstractWordCount>463</abstractWordCount></qualityIndicators><title>Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d -electron count</title><pii><json:string>0022-328X(90)87268-I</json:string></pii><genre><json:string>research-article</json:string></genre><host><volume>394</volume><pii><json:string>S0022-328X(00)X1275-2</json:string></pii><pages><last>794</last><first>777</first></pages><issn><json:string>0022-328X</json:string></issn><issue>1–3</issue><genre><json:string>Journal</json:string></genre><language><json:string>unknown</json:string></language><title>Journal of Organometallic Chemistry</title><publicationDate>1990</publicationDate></host><categories><wos><json:string>CHEMISTRY, INORGANIC & NUCLEAR</json:string><json:string>CHEMISTRY, ORGANIC</json:string></wos></categories><publicationDate>1990</publicationDate><copyrightDate>1990</copyrightDate><doi><json:string>10.1016/0022-328X(90)87268-I</json:string></doi><id>E09722F8883EFAAA12C3C0B2457E7A345AC6AF63</id><score>1</score><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/E09722F8883EFAAA12C3C0B2457E7A345AC6AF63/fulltext/pdf</uri></json:item><json:item><original>true</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/E09722F8883EFAAA12C3C0B2457E7A345AC6AF63/fulltext/txt</uri></json:item><json:item><original>false</original><mimetype>application/zip</mimetype><extension>zip</extension><uri>https://api.istex.fr/document/E09722F8883EFAAA12C3C0B2457E7A345AC6AF63/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/E09722F8883EFAAA12C3C0B2457E7A345AC6AF63/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a">Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d -electron count</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>ELSEVIER</publisher><availability><p>ELSEVIER</p></availability><date>1990</date></publicationStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a">Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d -electron count</title><author><persName><forename type="first">Steve A.</forename><surname>Westcott</surname></persName><affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</affiliation></author><author><persName><forename type="first">Ashok K.</forename><surname>Kakkar</surname></persName><affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</affiliation></author><author><persName><forename type="first">Graham</forename><surname>Stringer</surname></persName><affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</affiliation></author><author><persName><forename type="first">Nicholas J.</forename><surname>Taylor</surname></persName><affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</affiliation></author><author><persName><forename type="first">Todd B.</forename><surname>Marder</surname></persName><affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</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)X1275-2</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1990"></date><biblScope unit="volume">394</biblScope><biblScope unit="issue">1–3</biblScope><biblScope unit="page" from="777">777</biblScope><biblScope unit="page" to="794">794</biblScope></imprint></monogr><idno type="istex">E09722F8883EFAAA12C3C0B2457E7A345AC6AF63</idno><idno type="DOI">10.1016/0022-328X(90)87268-I</idno><idno type="PII">0022-328X(90)87268-I</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>1990</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>The crystal and molecular structures of [(η-C9H7)2M] (M = Fe, 1; Co, 2; Ni, 3) and [(η-C9Me7)2Fe], 4, are reported, along with a discussion of the correlation between hapticity and the 13C chemical shift of the indenyl ring-junction carbons (C(3a), C(7a)). Single crystals of both 1 and 2 undergo non-destructive and reversible phase changes upon cooling below ca. 240–245 K. The room-temperature structures are disordered; however, the low temperature ones (150 K) are essentially ordered. Crystals of 3 do not display this behavior on cooling to 150 K, and residual anisotropy in certain carbon atoms is ascribed to a minor twinning problem. Crystals of 4 were only examined at ambient temperature, where an ordered structure was obtained. In contrast to the analogous Cp2M series (Cp = η5-C5H5; M = Fe, Co, Ni), which display a gradual symmetric increase in MC distances in the order Fe < Co < Ni, the distortions in the indenyl series are of a fundamentally different nature. Thus, there is a gradual increase in the degree of slip-fold distortion from η5- toward η3-coordination which involves (a) slippage of the metal away from C(3a),C(7a), and (b) folding of the ring system (particularly at C(1),C(3)), in the order Fe < Co < Ni. The slip values (Δ = avg d(MC(3a),C(7a)) − avg d(MC(1),C(3)) are 0.043(4), 0.124(4), 0.418(6), and 0.030(4) Å for 1–4, respectively. For a “true η5”-complex, Δ should be ca. 0 Å, whereas values of ca. 0.69–0.79 Å have been reported for “true η3-”indenyl complexes such as [(η3-C9H7)Ir(PMe2Ph)3]. Therefore, complexes 1 and 4 are clearly η5, as predicted on the basis of the 18-electron rule, whereas 2 and 3 display increasing degrees of distortion in both rings to avoid 19- and 20-electron counts, respectively. The two indenyl rings in 3 are half-way between η5- and η3-coordination modes. Crystal data for 1 at 295 K are: monoclinic, P21 n, a 8.030(2), b 7.806(2), c 10.779(2) Å, β 107.39(1)°, V 648.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, Cc, a 16.021(4), b 15.510(5), c 11.187(3) Å, β 115.53(2)°, V 2509(1) Å3, Z = 8, R = 0.0306, Rw = 0.0332. For 2 at 295 K: monoclinic, P21 n, a 8.027(2), b 7.838(2), c 10.936(3) Å, β 107.57(2)°, V 655.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, P21 c, a 11.258(3), b 7.824(3), c 15.256(6) Å, β 108.07(2)°, V 1277.7(7) Å3, Z = 4, R = 0.0397, Rw = 0.0447. For 3, at 150 K: monoclinic, P21 n, a 6.063(1), b 20.056(3), c 10.703(2) Å, β 94.27(1)°, V 1297.9(3) Å3, Z = 4, R = 0.0413, Rw = 0.0493. For 4, at 295 K: orthorhombic, Pbcn, a 14.211(2), b 9.284(2), c 19.289(4) Å, V 2544.8(8) Å3, Z = 4, R = 0.0410, Rw = 0.0421.</p></abstract></profileDesc><revisionDesc><change when="1990-02-13">Received</change><change when="1990">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>9087268I</aid><ce:pii>0022-328X(90)87268-I</ce:pii><ce:doi>10.1016/0022-328X(90)87268-I</ce:doi><ce:copyright type="unknown" year="1990"></ce:copyright></item-info><head><ce:title>Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C<ce:inf>9</ce:inf>R<ce:inf>7</ce:inf>)<ce:inf>2</ce:inf>M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of <ce:italic>d</ce:italic>-electron count</ce:title><ce:author-group><ce:author><ce:given-name>Steve A.</ce:given-name><ce:surname>Westcott</ce:surname></ce:author><ce:author><ce:given-name>Ashok K.</ce:given-name><ce:surname>Kakkar</ce:surname></ce:author><ce:author><ce:given-name>Graham</ce:given-name><ce:surname>Stringer</ce:surname></ce:author><ce:author><ce:given-name>Nicholas J.</ce:given-name><ce:surname>Taylor</ce:surname><ce:ranking><ce:sup>∗</ce:sup></ce:ranking></ce:author><ce:author><ce:given-name>Todd B.</ce:given-name><ce:surname>Marder</ce:surname><ce:ranking><ce:sup>∗</ce:sup></ce:ranking></ce:author><ce:affiliation><ce:textfn>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</ce:textfn></ce:affiliation></ce:author-group><ce:date-received day="13" month="2" year="1990"></ce:date-received><ce:abstract><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>The crystal and molecular structures of [(η-C<ce:inf>9</ce:inf>H<ce:inf>7</ce:inf>)<ce:inf>2</ce:inf>M] (M = Fe, <ce:bold>1</ce:bold>; Co, <ce:bold>2</ce:bold>; Ni, <ce:bold>3</ce:bold>) and [(η-C<ce:inf>9</ce:inf>Me<ce:inf>7</ce:inf>)<ce:inf>2</ce:inf>Fe], <ce:bold>4</ce:bold>, are reported, along with a discussion of the correlation between hapticity and the <ce:sup loc="pre">13</ce:sup>C chemical shift of the indenyl ring-junction carbons (C(3a), C(7a)). Single crystals of both <ce:bold>1</ce:bold> and <ce:bold>2</ce:bold> undergo non-destructive and reversible phase changes upon cooling below ca. 240–245 K. The room-temperature structures are disordered; however, the low temperature ones (150 K) are essentially ordered. Crystals of <ce:bold>3</ce:bold> do not display this behavior on cooling to 150 K, and residual anisotropy in certain carbon atoms is ascribed to a minor twinning problem. Crystals of <ce:bold>4</ce:bold> were only examined at ambient temperature, where an ordered structure was obtained.</ce:simple-para><ce:simple-para>In contrast to the analogous Cp<ce:inf>2</ce:inf>M series (Cp = η<ce:sup>5</ce:sup>-C<ce:inf>5</ce:inf>H<ce:inf>5</ce:inf>; M = Fe, Co, Ni), which display a gradual symmetric increase in MC distances in the order Fe < Co < Ni, the distortions in the indenyl series are of a fundamentally different nature. Thus, there is a gradual increase in the degree of slip-fold distortion from η<ce:sup>5</ce:sup>- toward η<ce:sup>3</ce:sup>-coordination which involves (a) slippage of the metal away from C(3a),C(7a), and (b) folding of the ring system (particularly at C(1),C(3)), in the order Fe < Co < Ni.</ce:simple-para><ce:simple-para>The slip values (Δ = avg <ce:italic>d</ce:italic>(MC(3a),C(7a)) − avg <ce:italic>d</ce:italic>(MC(1),C(3)) are 0.043(4), 0.124(4), 0.418(6), and 0.030(4) Å for <ce:bold>1</ce:bold>–<ce:bold>4</ce:bold>, respectively. For a “true η<ce:sup>5</ce:sup>”-complex, Δ should be ca. 0 Å, whereas values of ca. 0.69–0.79 Å have been reported for “true η<ce:sup>3</ce:sup>-”indenyl complexes such as [(η<ce:sup>3</ce:sup>-C<ce:inf>9</ce:inf>H<ce:inf>7</ce:inf>)Ir(PMe<ce:inf>2</ce:inf>Ph)<ce:inf>3</ce:inf>]. Therefore, complexes <ce:bold>1</ce:bold> and <ce:bold>4</ce:bold> are clearly η<ce:sup>5</ce:sup>, as predicted on the basis of the 18-electron rule, whereas <ce:bold>2</ce:bold> and <ce:bold>3</ce:bold> display increasing degrees of distortion in both rings to avoid 19- and 20-electron counts, respectively. The two indenyl rings in <ce:bold>3</ce:bold> are half-way between η<ce:sup>5</ce:sup>- and η<ce:sup>3</ce:sup>-coordination modes.</ce:simple-para><ce:simple-para>Crystal data for <ce:bold>1</ce:bold> at 295 K are: monoclinic, <math altimg="si1.gif"><fr shape="sol"><nu><it>P</it>2<inf>1</inf></nu><de><it>n</it></de></fr></math>, <ce:italic>a</ce:italic> 8.030(2), <ce:italic>b</ce:italic> 7.806(2), <ce:italic>c</ce:italic> 10.779(2) Å, β 107.39(1)°, <ce:italic>V</ce:italic> 648.9(2) Å<ce:sup>3</ce:sup>, <ce:italic>Z</ce:italic> = 2, structure not refined; at 150 K: monoclinic, <ce:italic>Cc</ce:italic>, <ce:italic>a</ce:italic> 16.021(4), <ce:italic>b</ce:italic> 15.510(5), <ce:italic>c</ce:italic> 11.187(3) Å, β 115.53(2)°, <ce:italic>V</ce:italic> 2509(1) Å<ce:sup>3</ce:sup>, <ce:italic>Z</ce:italic> = 8, <ce:italic>R</ce:italic> = 0.0306, <ce:italic>R<ce:inf>w</ce:inf></ce:italic> = 0.0332. For <ce:bold>2</ce:bold> at 295 K: monoclinic, <math altimg="si2.gif"><fr shape="sol"><nu><it>P</it>2<inf>1</inf></nu><de><it>n</it></de></fr></math>, <ce:italic>a</ce:italic> 8.027(2), <ce:italic>b</ce:italic> 7.838(2), <ce:italic>c</ce:italic> 10.936(3) Å, β 107.57(2)°, <ce:italic>V</ce:italic> 655.9(2) Å<ce:sup>3</ce:sup>, <ce:italic>Z</ce:italic> = 2, structure not refined; at 150 K: monoclinic, <math altimg="si3.gif"><fr shape="sol"><nu><it>P</it>2<inf>1</inf></nu><de><it>c</it></de></fr></math>, <ce:italic>a</ce:italic> 11.258(3), <ce:italic>b</ce:italic> 7.824(3), <ce:italic>c</ce:italic> 15.256(6) Å, β 108.07(2)°, <ce:italic>V</ce:italic> 1277.7(7) Å<ce:sup>3</ce:sup>, <ce:italic>Z</ce:italic> = 4, <ce:italic>R</ce:italic> = 0.0397, <ce:italic>R<ce:inf>w</ce:inf></ce:italic> = 0.0447. For <ce:bold>3</ce:bold>, at 150 K: monoclinic, <math altimg="si4.gif"><fr shape="sol"><nu><it>P</it>2<inf>1</inf></nu><de><it>n</it></de></fr></math>, <ce:italic>a</ce:italic> 6.063(1), <ce:italic>b</ce:italic> 20.056(3), <ce:italic>c</ce:italic> 10.703(2) Å, β 94.27(1)°, <ce:italic>V</ce:italic> 1297.9(3) Å<ce:sup>3</ce:sup>, <ce:italic>Z</ce:italic> = 4, <ce:italic>R</ce:italic> = 0.0413, <ce:italic>R<ce:inf>w</ce:inf></ce:italic> = 0.0493. For <ce:bold>4</ce:bold>, at 295 K: orthorhombic, <ce:italic>Pbcn</ce:italic>, <ce:italic>a</ce:italic> 14.211(2), <ce:italic>b</ce:italic> 9.284(2), <ce:italic>c</ce:italic> 19.289(4) Å, <ce:italic>V</ce:italic> 2544.8(8) Å<ce:sup>3</ce:sup>, <ce:italic>Z</ce:italic> = 4, <ce:italic>R</ce:italic> = 0.0410, <ce:italic>R<ce:inf>w</ce:inf></ce:italic> = 0.0421.</ce:simple-para></ce:abstract-sec></ce:abstract></head></converted-article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo><title>Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d -electron count</title></titleInfo><titleInfo type="alternative" contentType="CDATA"><title>Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C</title></titleInfo><name type="personal"><namePart type="given">Steve A.</namePart><namePart type="family">Westcott</namePart><affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Ashok K.</namePart><namePart type="family">Kakkar</namePart><affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Graham</namePart><namePart type="family">Stringer</namePart><affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Nicholas J.</namePart><namePart type="family">Taylor</namePart><affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Todd B.</namePart><namePart type="family">Marder</namePart><affiliation>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 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">1990</dateIssued><dateCaptured encoding="w3cdtf">1990-02-13</dateCaptured><copyrightDate encoding="w3cdtf">1990</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 crystal and molecular structures of [(η-C9H7)2M] (M = Fe, 1; Co, 2; Ni, 3) and [(η-C9Me7)2Fe], 4, are reported, along with a discussion of the correlation between hapticity and the 13C chemical shift of the indenyl ring-junction carbons (C(3a), C(7a)). Single crystals of both 1 and 2 undergo non-destructive and reversible phase changes upon cooling below ca. 240–245 K. The room-temperature structures are disordered; however, the low temperature ones (150 K) are essentially ordered. Crystals of 3 do not display this behavior on cooling to 150 K, and residual anisotropy in certain carbon atoms is ascribed to a minor twinning problem. Crystals of 4 were only examined at ambient temperature, where an ordered structure was obtained. In contrast to the analogous Cp2M series (Cp = η5-C5H5; M = Fe, Co, Ni), which display a gradual symmetric increase in MC distances in the order Fe < Co < Ni, the distortions in the indenyl series are of a fundamentally different nature. Thus, there is a gradual increase in the degree of slip-fold distortion from η5- toward η3-coordination which involves (a) slippage of the metal away from C(3a),C(7a), and (b) folding of the ring system (particularly at C(1),C(3)), in the order Fe < Co < Ni. The slip values (Δ = avg d(MC(3a),C(7a)) − avg d(MC(1),C(3)) are 0.043(4), 0.124(4), 0.418(6), and 0.030(4) Å for 1–4, respectively. For a “true η5”-complex, Δ should be ca. 0 Å, whereas values of ca. 0.69–0.79 Å have been reported for “true η3-”indenyl complexes such as [(η3-C9H7)Ir(PMe2Ph)3]. Therefore, complexes 1 and 4 are clearly η5, as predicted on the basis of the 18-electron rule, whereas 2 and 3 display increasing degrees of distortion in both rings to avoid 19- and 20-electron counts, respectively. The two indenyl rings in 3 are half-way between η5- and η3-coordination modes. Crystal data for 1 at 295 K are: monoclinic, P21 n, a 8.030(2), b 7.806(2), c 10.779(2) Å, β 107.39(1)°, V 648.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, Cc, a 16.021(4), b 15.510(5), c 11.187(3) Å, β 115.53(2)°, V 2509(1) Å3, Z = 8, R = 0.0306, Rw = 0.0332. For 2 at 295 K: monoclinic, P21 n, a 8.027(2), b 7.838(2), c 10.936(3) Å, β 107.57(2)°, V 655.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, P21 c, a 11.258(3), b 7.824(3), c 15.256(6) Å, β 108.07(2)°, V 1277.7(7) Å3, Z = 4, R = 0.0397, Rw = 0.0447. For 3, at 150 K: monoclinic, P21 n, a 6.063(1), b 20.056(3), c 10.703(2) Å, β 94.27(1)°, V 1297.9(3) Å3, Z = 4, R = 0.0413, Rw = 0.0493. For 4, at 295 K: orthorhombic, Pbcn, a 14.211(2), b 9.284(2), c 19.289(4) Å, V 2544.8(8) Å3, Z = 4, R = 0.0410, Rw = 0.0421.</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">19900811</dateIssued></originInfo><identifier type="ISSN">0022-328X</identifier><identifier type="PII">S0022-328X(00)X1275-2</identifier><part><date>19900811</date><detail type="volume"><number>394</number><caption>vol.</caption></detail><detail type="issue"><number>1–3</number><caption>no.</caption></detail><extent unit="issue pages"><start>C1</start><end>C48</end></extent><extent unit="issue pages"><start>1</start><end>794</end></extent><extent unit="pages"><start>777</start><end>794</end></extent></part></relatedItem><identifier type="istex">E09722F8883EFAAA12C3C0B2457E7A345AC6AF63</identifier><identifier type="DOI">10.1016/0022-328X(90)87268-I</identifier><identifier type="PII">0022-328X(90)87268-I</identifier><recordInfo><recordContentSource>ELSEVIER</recordContentSource></recordInfo></mods></metadata><enrichments><istex:catWosTEI uri="https://api.istex.fr/document/E09722F8883EFAAA12C3C0B2457E7A345AC6AF63/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)
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