dc.contributor.author | Konu, Jari | |
dc.contributor.author | Tuononen, Heikki | |
dc.contributor.author | Chivers, Tristram | |
dc.contributor.author | Corrente, Andrea | |
dc.contributor.author | Boeré, René | |
dc.contributor.author | Roemmele, Tracey | |
dc.date.accessioned | 2015-11-20T09:43:17Z | |
dc.date.available | 2015-11-20T09:43:17Z | |
dc.date.issued | 2008 | |
dc.identifier.citation | Konu, J., Tuononen, H., Chivers, T., Corrente, A., Boeré, R., & Roemmele, T. (2008). In Search of the [PhB(μ-NtBu)2]2As• Radical: Experimental and Computational Investigations of the Redox Chemistry of Group 15 Bis-boraamidinates. <i>Inorganic Chemistry</i>, <i>47</i>(9), 3823-3831. <a href="https://doi.org/10.1021/ic702435e" target="_blank">https://doi.org/10.1021/ic702435e</a> | |
dc.identifier.other | CONVID_18407512 | |
dc.identifier.other | TUTKAID_33804 | |
dc.identifier.uri | https://jyx.jyu.fi/handle/123456789/47768 | |
dc.description.abstract | DFT calculations for the group 15 radicals [PhB(μ-NtBu)2]2M• (M = P, As, Sb, Bi) predict a pnictogen-centered SOMO with smaller contributions to the unpaired spin density arising from the nitrogen and boron atoms. The reactions of Li2[PhB(μ-NR)2] (R = tBu, Dipp) with PCl3 afforded the unsolvated complex LiP[PhB(μ-NtBu)2]2 (1a) in low yield and ClP[PhB(μ-NDipp)2] (2), both of which were structurally characterized. Efforts to produce the arsenic-centered neutral radical, [PhB(μ-NtBu)2]2As•, via oxidation of LiAs[PhB(μ-NtBu)2]2 with one-half equivalent of SO2Cl2, yielded the Zwitterionic compound [PhB(μ-NtBu)2As(μ-NtBu)2B(Cl)Ph] (3) containing one four-coordinate boron center with a B−Cl bond. The reaction of 3 with GaCl3 produced the ion-separated salt, [PhB(μ-NtBu)2]2As+GaCl4− (4), which was characterized by X-ray crystallography. The reduction of 3 with sodium naphthalenide occurred by a two-electron process to give the corresponding anion [{PhB(μ-NtBu)2}2As]− as the sodium salt. Voltammetric investigations of 4 and LiAs[PhB(μ-NtBu)2]2 (1b) revealed irreversible processes. Attempts to generate the neutral radical [PhB(μ-NtBu)2]2As• from these ionic complexes via in situ electrolysis did not produce an EPR-active species. | |
dc.language.iso | eng | |
dc.publisher | ACS | |
dc.relation.ispartofseries | Inorganic Chemistry | |
dc.subject.other | boraamidinaatit | |
dc.subject.other | radikaalit | |
dc.subject.other | DFT | |
dc.subject.other | boraamidinates | |
dc.subject.other | radicals | |
dc.title | In Search of the [PhB(μ-NtBu)2]2As• Radical: Experimental and Computational Investigations of the Redox Chemistry of Group 15 Bis-boraamidinates | |
dc.type | article | |
dc.identifier.urn | URN:NBN:fi:jyu-201511193722 | |
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 | 2015-11-19T10:15:12Z | |
dc.type.coar | http://purl.org/coar/resource_type/c_2df8fbb1 | |
dc.description.reviewstatus | peerReviewed | |
dc.format.pagerange | 3823-3831 | |
dc.relation.issn | 0020-1669 | |
dc.relation.numberinseries | 9 | |
dc.relation.volume | 47 | |
dc.type.version | acceptedVersion | |
dc.rights.copyright | © 2008 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/ic702435e | |
dc.type.okm | A1 | |