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dc.contributor.authorArmstrong, Andrea
dc.contributor.authorChivers, Tristram
dc.contributor.authorTuononen, Heikki
dc.contributor.authorParvez, Masood
dc.date.accessioned2015-11-19T08:56:25Z
dc.date.available2015-11-19T08:56:25Z
dc.date.issued2005
dc.identifier.citationArmstrong, A., Chivers, T., Tuononen, H., & Parvez, M. (2005). Synthesis and Structures of Aluminum and Magnesium Complexes of Tetraimidophosphates and Trisamidothiophosphates: EPR and DFT Investigations of the Persistent Neutral Radicals {Me2Al[(μ-NR)(μ-NtBu)P(μ-NtBu)2]Li(THF)2}• (R = SiMe3, tBu). <i>Inorganic Chemistry</i>, <i>44</i>(16), 5778-5788. <a href="https://doi.org/10.1021/ic050689e" target="_blank">https://doi.org/10.1021/ic050689e</a>
dc.identifier.otherCONVID_15539483
dc.identifier.otherTUTKAID_18179
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/47742
dc.description.abstractReactions of (RNH)3PNSiMe3 (3a, R = tBu; 3b, R = Cy) with trimethylaluminum result in the formation of {Me2Al(μ-NtBu)(μ-NSiMe3)P(NHtBu)2]} (4) and the dimeric trisimidometaphosphate {Me2Al[(μ-NCy)(μ-NSiMe3)P(μ-NCy)2P(μ-NCy)(μ-NSiMe3)]AlMe2} (5a), respectively. The reaction of SP(NHtBu)3 (2a) with 1 or 2 equiv of AlMe3 yields {Me2Al[(μ-S)(μ-NtBu)P(NHtBu)2]} (7) and {Me2Al[(μ-S)(μ-NtBu)P(μ-NHtBu)(μ-NtBu)]AlMe2} (8), respectively. Metalation of 4 with nBuLi produces the heterobimetallic species {Me2Al[(μ-NtBu)(μ-NSiMe3)P(μ-NHtBu)(μ-NtBu)]Li(THF)2} (9a) and {[Me2Al][Li]2[P(NtBu)3(NSiMe3)]} (10) sequentially; in THF solutions, solvation of 10 yields an ion pair containing a spirocyclic tetraimidophosphate monoanion. Similarly, the reaction of (tBuNH)3PNtBu with AlMe3 followed by 2 equiv of nBuLi generates {Me2Al[(μ-NtBu)2P(μ2-NtBu)2(μ2-THF)[Li(THF)]2} (11a). Stoichiometric oxidations of 10 and 11a with iodine yield the neutral spirocyclic radicals {Me2Al[(μ-NR)(μ-NtBu)P(μ-NtBu)2]Li(THF)2}• (13a, R = SiMe3; 14a, R = tBu), which have been characterized by electron paramagnetic resonance spectroscopy. Density functional theory calculations confirm the retention of the spirocyclic structure and indicate that the spin density in these radicals is concentrated on the nitrogen atoms of the PN2Li ring. When 3a or 3b is treated with 0.5 equiv of dibutylmagnesium, the complexes {Mg[(μ-NtBu)(μ-NHtBu)P(NHtBu)(NSiMe3)]2} (15) and {Mg[(μ-NCy)(μ-NSiMe3)P(NHCy)2]2} (16) are obtained, respectively. The addition of 0.5 equiv of MgBu2 to 2a results in the formation of {Mg[(μ-S)(μ-NtBu)P(NHtBu)2]2} (17), which produces the hexameric species {[MgOH][(μ-S)(μ-NtBu)P(NHtBu)2]}6 (18) upon hydrolysis. Compounds 4, 5a, 7−11a, and 15−17 have been characterized by multinuclear (1H, 13C, and 31P) NMR spectroscopy and, in the case of 5a, 9a·2THF, 11a, and 18, by X-ray crystallography.
dc.language.isoeng
dc.publisherACS
dc.relation.ispartofseriesInorganic Chemistry
dc.subject.othertetraimidofosfaatit
dc.subject.othertrisamidotiofosfaatit
dc.subject.otherradikaalit
dc.subject.othertetraimidophosphates
dc.subject.othertrisamidothiophosphates
dc.subject.otherradicals
dc.titleSynthesis and Structures of Aluminum and Magnesium Complexes of Tetraimidophosphates and Trisamidothiophosphates: EPR and DFT Investigations of the Persistent Neutral Radicals {Me2Al[(μ-NR)(μ-NtBu)P(μ-NtBu)2]Li(THF)2}• (R = SiMe3, tBu)
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201511173690
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineEpäorgaaninen ja analyyttinen kemiafi
dc.contributor.oppiaineInorganic and Analytical Chemistryen
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.date.updated2015-11-17T16:15:04Z
dc.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.format.pagerange5778-5788
dc.relation.issn0020-1669
dc.relation.numberinseries16
dc.relation.volume44
dc.type.versionacceptedVersion
dc.rights.copyright© 2005 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
dc.rights.accesslevelopenAccessfi
dc.relation.doi10.1021/ic050689e
dc.type.okmA1


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