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dc.contributor.authorHossain, Md Kamal
dc.contributor.authorKöhntopp, Anja
dc.contributor.authorHaukka, Matti
dc.contributor.authorRichmond, Michael G.
dc.contributor.authorLehtonen, Ari
dc.contributor.authorNordlander, Ebbe
dc.date.accessioned2020-01-20T08:51:13Z
dc.date.available2020-01-20T08:51:13Z
dc.date.issued2020
dc.identifier.citationHossain, M. K., Köhntopp, A., Haukka, M., Richmond, M. G., Lehtonen, A., & Nordlander, E. (2020). Cis- and trans molybdenum oxo complexes of a prochiral tetradentate aminophenolate ligand : Synthesis, characterization and oxotransfer activity. <i>Polyhedron</i>, <i>178</i>, Article 114312. <a href="https://doi.org/10.1016/j.poly.2019.114312" target="_blank">https://doi.org/10.1016/j.poly.2019.114312</a>
dc.identifier.otherCONVID_33903876
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/67374
dc.description.abstractReaction of [MoO2Cl2(dmso)2] with the tetradentate O2N2 donor ligand papy [H2papy = N-(2-hydroxybenzyl)-N-(2-picolyl)glycine] leads to formation of the dioxomolybdenum(VI) complex [MoO2(papy)] (1) as a mixture of cis and trans isomers. Recrystallization from methanol furnishes solid cis-1, whereas the use of a dichloromethane-hexane mixture allows for the isolation of the trans-1 isomer. Both isomers have been structurally characterized by X-ray crystallography and the energy difference between the isomeric pair has been investigated by electronic structure calculations. Optimization of two configurational isomers in the gas phase predicts the trans isomer to lie 2.5 kcal/mol lower in energy (ΔG) than the cis isomer, which is inconsistent with the solution NMR data in d3-MeCN that exhibit a Keq of ca. 3 at 298 K for the trans⇌cis equilibrium. The DFT-computed energy difference is significantly improved (Keq = 5.4) by the inclusion of the MeCN solvent using the polarization continuum model (PCM). Density functional calculations reveal that the isomerization proceeds via a Ray-Dutt twist mechanism with a barrier of 14.5 kcal/mol, which is in accordance with the 1H NMR spectral data and the rapid equilibration of these isomers in solution. The catalytic reactivity of [MoO2(papy)] in the epoxidation of cis-cyclooctene is described, as well as its ability to effect oxo transfer from DMSO to PPh3.en
dc.format.mimetypeapplication/pdf
dc.languageeng
dc.language.isoeng
dc.publisherElsevier
dc.relation.ispartofseriesPolyhedron
dc.rightsCC BY-NC-ND 4.0
dc.subject.otherOxo Atom Transfer
dc.subject.otherepoxidation
dc.subject.othertripodal ligand
dc.subject.othervariable temperature NMR
dc.subject.othercomputational modelling
dc.titleCis- and trans molybdenum oxo complexes of a prochiral tetradentate aminophenolate ligand : Synthesis, characterization and oxotransfer activity
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-202001201314
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.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.relation.issn0277-5387
dc.relation.volume178
dc.type.versionacceptedVersion
dc.rights.copyright© 2020 Elsevier B.V.
dc.rights.accesslevelopenAccessfi
dc.format.contentfulltext
dc.rights.urlhttps://creativecommons.org/licenses/by-nc-nd/4.0/
dc.relation.doi10.1016/j.poly.2019.114312
jyx.fundinginformationThis research has been carried out within the framework of COST Action CM1003. MKH thanks the European Commission for an Erasmus Mundus predoctoral fellowship. MGR thanks the Robert A. Welch Foundation (Grant B-1093-MGR). Computational resources through the High Performance Computing Services and CASCaM at the University of North Texas are acknowledged. We also thank Dr. Göran Carlström (Lund University) for assistance with NMR measurements.
dc.type.okmA1


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