dc.contributor.author | Armstrong, Andrea | |
dc.contributor.author | Chivers, Tristram | |
dc.contributor.author | Tuononen, Heikki | |
dc.contributor.author | Parvez, Masood | |
dc.contributor.author | Boeré, René | |
dc.date.accessioned | 2015-11-18T11:44:59Z | |
dc.date.available | 2015-11-18T11:44:59Z | |
dc.date.issued | 2005 | |
dc.identifier.citation | Armstrong, 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.other | CONVID_15539662 | |
dc.identifier.other | TUTKAID_18180 | |
dc.identifier.uri | https://jyx.jyu.fi/handle/123456789/47731 | |
dc.description.abstract | The 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.iso | eng | |
dc.publisher | ACS | |
dc.relation.ispartofseries | Inorganic Chemistry | |
dc.subject.other | tetraimidofosfaatit | |
dc.subject.other | radikaalit | |
dc.subject.other | tetraimidophosphates | |
dc.subject.other | radicals | |
dc.title | Cubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)3(NR‘)]•2- | |
dc.type | article | |
dc.identifier.urn | URN:NBN:fi:jyu-201511173692 | |
dc.contributor.laitos | Kemian laitos | fi |
dc.contributor.laitos | Department of Chemistry | en |
dc.contributor.oppiaine | Epäorgaaninen ja analyyttinen kemia | fi |
dc.contributor.oppiaine | Inorganic and Analytical Chemistry | en |
dc.type.uri | http://purl.org/eprint/type/JournalArticle | |
dc.date.updated | 2015-11-17T16:15:09Z | |
dc.type.coar | http://purl.org/coar/resource_type/c_2df8fbb1 | |
dc.description.reviewstatus | peerReviewed | |
dc.format.pagerange | 7981-7991 | |
dc.relation.issn | 0020-1669 | |
dc.relation.numberinseries | 22 | |
dc.relation.volume | 44 | |
dc.type.version | acceptedVersion | |
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.accesslevel | openAccess | fi |
dc.relation.doi | 10.1021/ic051128q | |
dc.type.okm | A1 | |