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dc.contributor.authorArmstrong, Andrea
dc.contributor.authorChivers, Tristram
dc.contributor.authorTuononen, Heikki
dc.contributor.authorParvez, Masood
dc.contributor.authorBoeré, René
dc.date.accessioned2015-11-18T11:44:59Z
dc.date.available2015-11-18T11:44:59Z
dc.date.issued2005
dc.identifier.citationArmstrong, A., Chivers, T., Tuononen, H., Parvez, M., & Boeré, R. (2005). Cubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)3(NR‘)]•2-. <i>Inorganic Chemistry</i>, <i>44</i>(22), 7981-7991. <a href="https://doi.org/10.1021/ic051128q" target="_blank">https://doi.org/10.1021/ic051128q</a>
dc.identifier.otherCONVID_15539662
dc.identifier.otherTUTKAID_18180
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/47731
dc.description.abstractThe reaction of Cl3PNSiMe3 with 3 equiv of LiHNR (R = iPr, Cy, tBu, Ad) in diethyl ether produces the corresponding tris(amino)(imino)phosphoranes (RNH)3PNSiMe3 (1a, R = iPr; 1b, R = Cy; 1c, R = tBu; 1d, R = Ad); subsequent reactions of 1b−d with nBuLi yield the trilithiated tetraimidophosphates {Li3[P(NR)3(NSiMe3)]} (2a, R = Cy; 2b, R = tBu; 2c, R = Ad). The reaction of [(tBuNH)4P]Cl with 1 equiv of nBuLi results in the isolation of (tBuNH)3PNtBu (1e); treatment of 1e with additional nBuLi generates the symmetrical tetraimidophosphate {Li3[P(NtBu)4]} (2d). Compounds 1 and 2 have been characterized by multinuclear (1H, 13C, and 31P) NMR spectroscopy; X-ray structures of 1b,c were also obtained. Oxidations of 2a−c with iodine, bromine, or sulfuryl chloride produces transient radicals in the case of 2a or stable radicals of the formula {Li2[P(NR)3(NSiMe3)]LiX·3THF}• (X = Cl, Br, I; R = tBu, Ad). The stable radicals exhibit C3 symmetry and are thought to exist in a cubic arrangement, with the monomeric LiX unit bonded to the neutral radical {Li2[P(NR)3(NSiMe3)]}• to complete the Li3N3PX cube. Reactions of solvent-separated ion pair {[Li(THF)4]{Li(THF)2[(μ-NtBu)2P(μ-NtBu)2]Li(THF)2} (6) with I2 or SO2Cl2 produce the persistent spirocyclic radical {(THF)2Li(μ-NtBu)2P(μ-NtBu)Li(THF)2}• (10a); all radicals have been characterized by a combination of variable concentration EPR experiments and DFT calculations.
dc.language.isoeng
dc.publisherACS
dc.relation.ispartofseriesInorganic Chemistry
dc.subject.othertetraimidofosfaatit
dc.subject.otherradikaalit
dc.subject.othertetraimidophosphates
dc.subject.otherradicals
dc.titleCubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)3(NR‘)]•2-
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201511173692
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.updated2015-11-17T16:15:09Z
dc.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.format.pagerange7981-7991
dc.relation.issn0020-1669
dc.relation.numberinseries22
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/ic051128q
dc.type.okmA1


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