NMR Spectroscopic Evidence for the Intermediacy of XeF3– in XeF2/F– Exchange, Attempted Syntheses and Thermochemistry of XeF3– Salts, and Theoretical Studies of the XeF3– Anion
dc.contributor.author | Vasdev, Neil | |
dc.contributor.author | Moran, Matthew | |
dc.contributor.author | Chirakal, Raman | |
dc.contributor.author | Tuononen, Heikki | |
dc.contributor.author | Suontamo, Reijo | |
dc.contributor.author | Bain, Alex | |
dc.contributor.author | Schrobilgen, Gary | |
dc.date.accessioned | 2015-11-25T11:52:21Z | |
dc.date.available | 2015-11-25T11:52:21Z | |
dc.date.issued | 2010 | |
dc.identifier.citation | Vasdev, N., Moran, M., Chirakal, R., Tuononen, H., Suontamo, R., Bain, A., & Schrobilgen, G. (2010). NMR Spectroscopic Evidence for the Intermediacy of XeF3– in XeF2/F– Exchange, Attempted Syntheses and Thermochemistry of XeF3– Salts, and Theoretical Studies of the XeF3– Anion. <i>Inorganic Chemistry</i>, <i>49</i>(19), 8997-9004. <a href="https://doi.org/10.1021/ic101275m" target="_blank">https://doi.org/10.1021/ic101275m</a> | |
dc.identifier.other | CONVID_20145015 | |
dc.identifier.other | TUTKAID_43887 | |
dc.identifier.uri | https://jyx.jyu.fi/handle/123456789/47825 | |
dc.description.abstract | The existence of the trifluoroxenate(II) anion, XeF3−, had been postulated in a prior NMR study of the exchange between fluoride ion and XeF2 in CH3CN solution. The enthalpy of activation for this exchange, ΔH⧧, has now been determined by use of single selective inversion 19F NMR spectroscopy to be 74.1 ± 5.0 kJ mol−1 (0.18 M) and 56.9 ± 6.7 kJ mol−1 (0.36 M) for equimolar amounts of [N(CH3)4][F] and XeF2 in CH3CN solvent. Although the XeF3− anion has been observed in the gas phase, attempts to prepare the Cs+ and N(CH3)4+ salts of XeF3− have been unsuccessful, and are attributed to the low fluoride ion affinity of XeF2 and fluoride ion solvation in CH3CN solution. The XeF3− anion would represent the first example of an AX3E3 valence shell electron pair repulsion (VSEPR) arrangement of electron lone pair and bond pair domains. Fluorine-19 exchange between XeF2 and the F− anion has also been probed computationally using coupled-cluster singles and doubles (CCSD) and density functional theory (DFT; PBE1PBE) methods. The energy-minimized geometry of the ground state shows that the F− anion is only weakly coordinated to XeF2 (F2Xe---F−; a distorted Y-shape possessing Cs symmetry), while the XeF3− anion exists as a first-order transition state in the fluoride ion exchange mechanism, and is planar and Y-shaped (C2v symmetry). The molecular geometry and bonding of the XeF3− anion has been described and rationalized in terms of electron localization function (ELF) calculations, as well as the VSEPR model of molecular geometry. Quantum-chemical calculations, using the CCSD method and a continuum solvent model for CH3CN, accurately reproduced the transition-state enthalpy observed by 19F NMR spectroscopy, and showed a negative but negligible enthalpy for the formation of the F2Xe---F− adduct in this medium. | |
dc.language.iso | eng | |
dc.publisher | ACS | |
dc.relation.ispartofseries | Inorganic Chemistry | |
dc.subject.other | ksenon fluoridit | |
dc.subject.other | xenon fluorides | |
dc.title | NMR Spectroscopic Evidence for the Intermediacy of XeF3– in XeF2/F– Exchange, Attempted Syntheses and Thermochemistry of XeF3– Salts, and Theoretical Studies of the XeF3– Anion | |
dc.type | article | |
dc.identifier.urn | URN:NBN:fi:jyu-201511243774 | |
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 | 2015-11-24T07:15:11Z | |
dc.type.coar | http://purl.org/coar/resource_type/c_2df8fbb1 | |
dc.description.reviewstatus | peerReviewed | |
dc.format.pagerange | 8997-9004 | |
dc.relation.issn | 0020-1669 | |
dc.relation.numberinseries | 19 | |
dc.relation.volume | 49 | |
dc.type.version | acceptedVersion | |
dc.rights.copyright | © 2010 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/ic101275m | |
dc.type.okm | A1 |