dc.contributor.author | LaPierre, Etienne A. | |
dc.contributor.author | Watanabe, Lara K. | |
dc.contributor.author | Patrick, Brian O. | |
dc.contributor.author | Rawson, Jeremy M. | |
dc.contributor.author | Tuononen, Heikki M. | |
dc.contributor.author | Manners, Ian | |
dc.date.accessioned | 2023-11-15T08:50:52Z | |
dc.date.available | 2023-11-15T08:50:52Z | |
dc.date.issued | 2023 | |
dc.identifier.citation | LaPierre, E. A., Watanabe, L. K., Patrick, B. O., Rawson, J. M., Tuononen, H. M., & Manners, I. (2023). Synthesis of a Carbene-Stabilized (Diphospha)aminyl Radical and Its One Electron Oxidation and Reduction to Nonclassical Nitrenium and Amide Species. <i>Journal of the American Chemical Society</i>, <i>145</i>(16), 9223-9232. <a href="https://doi.org/10.1021/jacs.3c01408" target="_blank">https://doi.org/10.1021/jacs.3c01408</a> | |
dc.identifier.other | CONVID_182820771 | |
dc.identifier.uri | https://jyx.jyu.fi/handle/123456789/91925 | |
dc.description.abstract | Herein, we report the synthesis of an acyclic carbene-stabilized diphospha(aminyl) PNP radical CAACMePNPCAACMe4 (CAACMe = 1-[2,6-bis(isopropyl)phenyl]-3,3,5,5-tetramethyl-2-pyrrolidinylidene) by a facile one-pot, seven-electron reduction of hexachlorophosphazene chloride [Cl3PNPCl3][Cl]. The PNP radical 4 features a conjugated framework with spin density primarily localized on the central nitrogen atom as well as the flanking carbenes. Unlike other tripnictogen radicals, 4 undergoes facile one-electron oxidation and reduction to yield nonclassical nitrenium and amide species [5]+ and [6]−, respectively. The cation [5]+ exhibits conformational flexibility in the solution state between the expected W-shaped geometry [5b]+ and a previously unobserved linear heteroallene-type structure [5a]+, which was characterized in the solid state. The equilibrium was explored both computationally and experimentally, showing that [5a]+ is favored over [5b]+ both enthalpically (ΔH = −2.9 × 103 ± 80 J mol–1) and entropically (ΔS = 4.2 ± 0.25 J mol–1 K–1). The formal amide [6]− displays remarkable flexibility in its coordination chemistry due to the presence of multiple Lewis basic centers, as evidenced by the structure of its potassium complex K262, which exhibits μ, κ-P, κ-P, and η3-PNP coordination modes. Protonation of [6]− leads to the formation of an amine 7, which features a trigonal planar geometry around nitrogen. | en |
dc.format.mimetype | application/pdf | |
dc.language.iso | eng | |
dc.publisher | American Chemical Society (ACS) | |
dc.relation.ispartofseries | Journal of the American Chemical Society | |
dc.rights | In Copyright | |
dc.subject.other | carbene compounds | |
dc.subject.other | mathematical methods | |
dc.subject.other | nitrogen | |
dc.subject.other | potassium | |
dc.subject.other | redox reactions | |
dc.title | Synthesis of a Carbene-Stabilized (Diphospha)aminyl Radical and Its One Electron Oxidation and Reduction to Nonclassical Nitrenium and Amide Species | |
dc.type | article | |
dc.identifier.urn | URN:NBN:fi:jyu-202311157943 | |
dc.contributor.laitos | Kemian laitos | fi |
dc.contributor.laitos | Department of Chemistry | en |
dc.contributor.oppiaine | Epäorgaaninen ja analyyttinen kemia | fi |
dc.contributor.oppiaine | Nanoscience Center | fi |
dc.contributor.oppiaine | Epäorgaaninen kemia | fi |
dc.contributor.oppiaine | Inorganic and Analytical Chemistry | en |
dc.contributor.oppiaine | Nanoscience Center | en |
dc.contributor.oppiaine | Inorganic Chemistry | en |
dc.type.uri | http://purl.org/eprint/type/JournalArticle | |
dc.type.coar | http://purl.org/coar/resource_type/c_2df8fbb1 | |
dc.description.reviewstatus | peerReviewed | |
dc.format.pagerange | 9223–9232 | |
dc.relation.issn | 0002-7863 | |
dc.relation.numberinseries | 16 | |
dc.relation.volume | 145 | |
dc.type.version | acceptedVersion | |
dc.rights.copyright | © 2023 American Chemical Society | |
dc.rights.accesslevel | openAccess | fi |
dc.subject.yso | typpi | |
dc.subject.yso | kalium | |
dc.subject.yso | matemaattiset menetelmät | |
dc.subject.yso | hapetus-pelkistysreaktio | |
dc.format.content | fulltext | |
jyx.subject.uri | http://www.yso.fi/onto/yso/p10988 | |
jyx.subject.uri | http://www.yso.fi/onto/yso/p11555 | |
jyx.subject.uri | http://www.yso.fi/onto/yso/p1880 | |
jyx.subject.uri | http://www.yso.fi/onto/yso/p28877 | |
dc.rights.url | http://rightsstatements.org/page/InC/1.0/?language=en | |
dc.relation.doi | 10.1021/jacs.3c01408 | |
jyx.fundinginformation | I.M. thanks the Canadian Government for a Canada 150 Research Chair, NSERC for a Discovery Grant, and the University of Victoria for start-up funds. E.L. thanks the NSERC for a Postdoctoral Fellowship. H.M.T. thanks the University of Jyväskylä for financial support and acknowledges a grant of computing capacity from the Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:researchinfras-2016072533). J.M.R. thanks the NSERC for financial support through a Discovery Grant (2020-04627). | |
dc.type.okm | A1 | |