Photochemistry of (η3-allyl)tricarbonyecobaet in frozen gas matrices at 12 K. Infrared spectroscopic evidence for the formation of (η3-allyl) dicarbonylcobalt, (η3-allyl)dicarbonyl(dinitrogen)cobalt, (σ-allyl)tetracarbonylcobalt, and tetracarbonylcobalt complexes
Identifieur interne : 004813 ( Istex/Curation ); précédent : 004812; suivant : 004814Photochemistry of (η3-allyl)tricarbonyecobaet in frozen gas matrices at 12 K. Infrared spectroscopic evidence for the formation of (η3-allyl) dicarbonylcobalt, (η3-allyl)dicarbonyl(dinitrogen)cobalt, (σ-allyl)tetracarbonylcobalt, and tetracarbonylcobalt complexes
Auteurs : Antony J. Rest ; David J. TaylorSource :
- Journal of the Chemical Society, Dalton Transactions [ 0300-9246 ] ; 1983.
Abstract
Infrared spectroscopic evidence is presented to show that photolysis of [Co(η3-allyl)(CO)3] in gas matrices at 12 K gives [Co(η3-allyl)(CO)2](in Ar or CH4), [Co(η3-allyl)(CO)2(N2)](in N2), and [Co(σ-allyl)(CO)4] followed by [Co(CO)4](in CO). The detection of [Co(η3-allyl)(CO)2] is consistent with the results of kinetic studies, which have been interpreted in terms of a dissociative path and a co-ordinatively unsaturated intermediate in the thermal CO substitution reactions, and theoretical calculations which show a low M–C(O) bond order a detection of [Co(σ-allyl)(CO)4] and the reversibility of the reaction [Co(η3-allyl)(CO)3]+ CO ⇄[Co(σ-allyl)(CO)4] suggest that there may be a contribution to the reactivity of [Co(η3-allyl)(CO)3] from the hitherto neglected associative path.
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DOI: 10.1039/DT9830001291
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<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title>Photochemistry of (η3-allyl)tricarbonyecobaet in frozen gas matrices at 12 K. Infrared spectroscopic evidence for the formation of (η3-allyl) dicarbonylcobalt, (η3-allyl)dicarbonyl(dinitrogen)cobalt, (σ-allyl)tetracarbonylcobalt, and tetracarbonylcobalt complexes</title><author wicri:is="90%"><name sortKey="Rest, Antony J" sort="Rest, Antony J" uniqKey="Rest A" first="Antony J." last="Rest">Antony J. Rest</name></author><author wicri:is="90%"><name sortKey="Taylor, David J" sort="Taylor, David J" uniqKey="Taylor D" first="David J." last="Taylor">David J. Taylor</name></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:07642A2D958ACA0570A1F8C6D7257DB2549DA4E2</idno><date when="1983" year="1983">1983</date><idno type="doi">10.1039/DT9830001291</idno><idno type="url">https://api.istex.fr/document/07642A2D958ACA0570A1F8C6D7257DB2549DA4E2/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">004813</idno><idno type="wicri:Area/Istex/Curation">004813</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a">Photochemistry of (η3-allyl)tricarbonyecobaet in frozen gas matrices at 12 K. Infrared spectroscopic evidence for the formation of (η3-allyl) dicarbonylcobalt, (η3-allyl)dicarbonyl(dinitrogen)cobalt, (σ-allyl)tetracarbonylcobalt, and tetracarbonylcobalt complexes</title><author wicri:is="90%"><name sortKey="Rest, Antony J" sort="Rest, Antony J" uniqKey="Rest A" first="Antony J." last="Rest">Antony J. Rest</name></author><author wicri:is="90%"><name sortKey="Taylor, David J" sort="Taylor, David J" uniqKey="Taylor D" first="David J." last="Taylor">David J. Taylor</name></author></analytic><monogr></monogr><series><title level="j">Journal of the Chemical Society, Dalton Transactions</title><title level="j" type="abbrev">J. Chem. Soc., Dalton Trans.</title><idno type="ISSN">0300-9246</idno><idno type="eISSN">1364-5447</idno><imprint><publisher>The Royal Society of Chemistry.</publisher><date type="published" when="1983">1983</date><biblScope unit="volume">0</biblScope><biblScope unit="issue">7</biblScope><biblScope unit="page" from="1291">1291</biblScope><biblScope unit="page" to="1298">1298</biblScope></imprint><idno type="ISSN">0300-9246</idno></series><idno type="istex">07642A2D958ACA0570A1F8C6D7257DB2549DA4E2</idno><idno type="DOI">10.1039/DT9830001291</idno><idno type="ms-id">DT9830001291</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0300-9246</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract">Infrared spectroscopic evidence is presented to show that photolysis of [Co(η3-allyl)(CO)3] in gas matrices at 12 K gives [Co(η3-allyl)(CO)2](in Ar or CH4), [Co(η3-allyl)(CO)2(N2)](in N2), and [Co(σ-allyl)(CO)4] followed by [Co(CO)4](in CO). The detection of [Co(η3-allyl)(CO)2] is consistent with the results of kinetic studies, which have been interpreted in terms of a dissociative path and a co-ordinatively unsaturated intermediate in the thermal CO substitution reactions, and theoretical calculations which show a low M–C(O) bond order a detection of [Co(σ-allyl)(CO)4] and the reversibility of the reaction [Co(η3-allyl)(CO)3]+ CO ⇄[Co(σ-allyl)(CO)4] suggest that there may be a contribution to the reactivity of [Co(η3-allyl)(CO)3] from the hitherto neglected associative path.</div></front></TEI></record>Pour manipuler ce document sous Unix (Dilib)
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