Model compounds for polymeric redox-switchable hemilabile ligands
Identifieur interne : 004252 ( Istex/Curation ); précédent : 004251; suivant : 004253Model compounds for polymeric redox-switchable hemilabile ligands
Auteurs : Thomas B. Higgins [États-Unis] ; Chad A. Mirkin [États-Unis]Source :
- Inorganica Chimica Acta [ 0020-1693 ] ; 1995.
Abstract
The syntheses and characterization of two new tetradentate hemilabile ligands 1,2-bis(2-diphenylphosphinoethoxy)benzene (5) and 2,2′-bis(2-diphenylphosphinoethoxy)-1,1′-binaphthalene (10) are reported. Ligands 5 and 10 were synthesized as models to test the suitability of specific phosphinoether coordination environments for complexing Rh(I) in high surface area thiophene-based, redox-active polymeric systems. Ligands 5 and 10 react with the product formed from the reaction between (bicyclo[2.2.1]hepta-2,5-diene)rhodium(I) chloride dimer and AgBF4 to form [η2-(1,2-bis(2-diphenylphosphinoethoxy)benzene) η4-norbornadiene rhodium(I)] tetrafluoroborate (6) and [η2-(2,2′-bis(2-diphenylphosphinoethoxy)-1,1′-binaphthalene) η4-norbornadiene rhodium(I)] tetrafluoroborate (11), respectively. Complexes 6 and 11 react with H2 in CD2Cl2 to form the two new square-planar cis-phosphine, cis-ether Rh(I) complexes 7 and 12, respectively. Compound 7, which could be characterized on the basis of its 31P NMR spectrum, is extremely reactive and decomposes in CD2Cl2. In THF compounds 6 and 11 react with H2 to form the dihydride, bis-THF adducts 8 and 16, respectively, which upon removal of solvent form 7 and 12, respectively. Compound 12 is a stable, isolable complex that reacts with acetonitrile to form a cis-phosphine, cis-acetonitrile adduct 15. Removal of solvent from 15 leads to the quantitative reformation of 12. Compound 12 does not react to a detectable extent with gross excesses of benzene or even thiophene, demonstrating the suitability of this ligand environment for implementation into a thiophene-based polymeric system. Compound 12 does catalyze the hydrogenation of cyclohexene to form cyclohexane, and mechanistic implications of such a transformation are discussed.
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DOI: 10.1016/0020-1693(95)04553-8
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Mirkin</name><affiliation wicri:level="1"><mods:affiliation>Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, IL 60208, USA</mods:affiliation><country xml:lang="fr">États-Unis</country><wicri:regionArea>Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, IL 60208</wicri:regionArea></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:60871DFE4970B55299AA56FC03D0691019D65F07</idno><date when="1995" year="1995">1995</date><idno type="doi">10.1016/0020-1693(95)04553-8</idno><idno type="url">https://api.istex.fr/document/60871DFE4970B55299AA56FC03D0691019D65F07/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">004252</idno><idno type="wicri:Area/Istex/Curation">004252</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a">Model compounds for polymeric redox-switchable hemilabile ligands</title><author><name sortKey="Higgins, Thomas B" sort="Higgins, Thomas B" uniqKey="Higgins T" first="Thomas B." last="Higgins">Thomas B. Higgins</name><affiliation wicri:level="1"><mods:affiliation>Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, IL 60208, USA</mods:affiliation><country xml:lang="fr">États-Unis</country><wicri:regionArea>Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, IL 60208</wicri:regionArea></affiliation></author><author><name sortKey="Mirkin, Chad A" sort="Mirkin, Chad A" uniqKey="Mirkin C" first="Chad A." last="Mirkin">Chad A. Mirkin</name><affiliation wicri:level="1"><mods:affiliation>Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, IL 60208, USA</mods:affiliation><country xml:lang="fr">États-Unis</country><wicri:regionArea>Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, IL 60208</wicri:regionArea></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="1995">1995</date><biblScope unit="volume">240</biblScope><biblScope unit="issue">1–2</biblScope><biblScope unit="page" from="347">347</biblScope><biblScope unit="page" to="353">353</biblScope></imprint><idno type="ISSN">0020-1693</idno></series><idno type="istex">60871DFE4970B55299AA56FC03D0691019D65F07</idno><idno type="DOI">10.1016/0020-1693(95)04553-8</idno><idno type="PII">0020-1693(95)04553-8</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0020-1693</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The syntheses and characterization of two new tetradentate hemilabile ligands 1,2-bis(2-diphenylphosphinoethoxy)benzene (5) and 2,2′-bis(2-diphenylphosphinoethoxy)-1,1′-binaphthalene (10) are reported. Ligands 5 and 10 were synthesized as models to test the suitability of specific phosphinoether coordination environments for complexing Rh(I) in high surface area thiophene-based, redox-active polymeric systems. Ligands 5 and 10 react with the product formed from the reaction between (bicyclo[2.2.1]hepta-2,5-diene)rhodium(I) chloride dimer and AgBF4 to form [η2-(1,2-bis(2-diphenylphosphinoethoxy)benzene) η4-norbornadiene rhodium(I)] tetrafluoroborate (6) and [η2-(2,2′-bis(2-diphenylphosphinoethoxy)-1,1′-binaphthalene) η4-norbornadiene rhodium(I)] tetrafluoroborate (11), respectively. Complexes 6 and 11 react with H2 in CD2Cl2 to form the two new square-planar cis-phosphine, cis-ether Rh(I) complexes 7 and 12, respectively. Compound 7, which could be characterized on the basis of its 31P NMR spectrum, is extremely reactive and decomposes in CD2Cl2. In THF compounds 6 and 11 react with H2 to form the dihydride, bis-THF adducts 8 and 16, respectively, which upon removal of solvent form 7 and 12, respectively. Compound 12 is a stable, isolable complex that reacts with acetonitrile to form a cis-phosphine, cis-acetonitrile adduct 15. Removal of solvent from 15 leads to the quantitative reformation of 12. Compound 12 does not react to a detectable extent with gross excesses of benzene or even thiophene, demonstrating the suitability of this ligand environment for implementation into a thiophene-based polymeric system. Compound 12 does catalyze the hydrogenation of cyclohexene to form cyclohexane, and mechanistic implications of such a transformation are discussed.</div></front></TEI></record>Pour manipuler ce document sous Unix (Dilib)
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