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dc.contributor.authorKonu, Jari
dc.contributor.authorChivers, Tristram
dc.contributor.authorTuononen, Heikki
dc.date.accessioned2015-11-20T08:35:01Z
dc.date.available2015-11-20T08:35:01Z
dc.date.issued2006
dc.identifier.citationKonu, J., Chivers, T., & Tuononen, H. (2006). Synthesis, Spectroscopic, and Structural Investigation of the Cyclic [N(PR2E)2]+ Cations (E = Se, Te; R = iPr, Ph): the Effect of Anion and R-Group Exchange. <i>Inorganic Chemistry</i>, <i>45</i>(26), 10678-10687. <a href="https://doi.org/10.1021/ic061545i" target="_blank">https://doi.org/10.1021/ic061545i</a>
dc.identifier.otherCONVID_16479696
dc.identifier.otherTUTKAID_23551
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/47763
dc.description.abstractTwo-electron oxidation of the [N(PiPr2E)2]- anion with iodine produces the cyclic [N(PiPr2E)2]+ (E = Se, Te) cations, which exhibit long E−E bonds in the iodide salts [N(PiPr2Se)2]I (4) and [N(PiPr2Te)2]I (5). The iodide salts 4 and 5 are converted to the ion-separated salts [N(PiPr2Se)2]SbF6 (6) and [N(PiPr2Te)2]SbF6 (7) upon treatment with AgSbF6. Compounds 4−7 were characterized in solution by multinuclear NMR, vibrational, and UV−visible spectroscopy supported by DFT calculations. A structural comparison of salts 4−7 and [N(PiPr2Te)2]Cl (8) confirms that the long E−E bonds in 4, 5, and 8 can be attributed primarily to the donation of electron density from a lone pair of the halide counterion into the E−E σ* orbital (LUMO) of the cation. The phenyl derivative [N(PPh2Te)2]I (9) was prepared in a similar manner. However, the attempted synthesis of the selenium analogue, [N(PPh2Se)2]I, produced a 1:1 mixture of [N(PPh2Se)2(μ-Se)][I] (10) and [SeP(Ph2)N(Ph2)PI] (11). DFT calculations of the formation energies of 10 and 11 support the observed decomposition. Compound 10 is a centrosymmetric dimer in which two six-membered NP2Se3 rings are bridged by two I- anions. Compound 11 produces the nine-atom chain {[N(PPh2)2Se]2(μ-O)} (12) upon hydrolysis during crystallization. The reaction between [(TMEDA)NaN(PiPr2Se)2] and SeCl2 in a 1:1 molar ratio yields the related acyclic species [SeP(iPr2)N(iPr2)PCl] (13), which was characterized by multinuclear NMR spectroscopy and an X-ray structural determination.
dc.language.isoeng
dc.publisherACS
dc.relation.ispartofseriesInorganic Chemistry
dc.subject.otherdikalkogenoimidodifosfinaatit
dc.subject.otherdichalcogenoimidodiphosphinates
dc.titleSynthesis, Spectroscopic, and Structural Investigation of the Cyclic [N(PR2E)2]+ Cations (E = Se, Te; R = iPr, Ph): the Effect of Anion and R-Group Exchange
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201511183698
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.updated2015-11-18T10:15:07Z
dc.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.format.pagerange10678-10687
dc.relation.issn0020-1669
dc.relation.numberinseries26
dc.relation.volume45
dc.type.versionacceptedVersion
dc.rights.copyright© 2006 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.subject.ysoligandit
jyx.subject.urihttp://www.yso.fi/onto/yso/p24741
dc.relation.doi10.1021/ic061545i
dc.type.okmA1


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