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dc.contributor.authorKamal, Hossain Md.
dc.contributor.authorSchachner, Jörg A.
dc.contributor.authorHaukka, Matti
dc.contributor.authorRichmond, Michael G.
dc.contributor.authorMösch-Zanetti, Nadia C.
dc.contributor.authorLehtonen, Ari
dc.contributor.authorNordlander, Ebbe
dc.date.accessioned2021-06-02T06:48:13Z
dc.date.available2021-06-02T06:48:13Z
dc.date.issued2021
dc.identifier.citationKamal, H. M., Schachner, J. A., Haukka, M., Richmond, M. G., Mösch-Zanetti, N. C., Lehtonen, A., & Nordlander, E. (2021). Oxygen Atom Transfer Catalysis by Dioxidomolybdenum(VI) Complexes of Pyridyl Aminophenolate Ligands. <i>Polyhedron</i>, <i>205</i>, Article 115234. <a href="https://doi.org/10.1016/j.poly.2021.115234" target="_blank">https://doi.org/10.1016/j.poly.2021.115234</a>
dc.identifier.otherCONVID_68070831
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/76141
dc.description.abstractA series of new cationic dioxidomolybdenum(VI) complexes [MoO2(Ln)]PF6 (2-5) with the tripodal tetradentate pyridyl aminophenolate ligands HL2-HL5 have been synthesized and characterized. Ligands HL2-HL4 carry substituents in the 4-position of the phenolate ring, viz. Cl, Br and NO2, respectively, whereas the ligand HL5, N-(2-hydroxy-3,5-di-tert-butylbenzyl)-N,N-bis(2-pyridylmethyl)amine, is a derivative of 3,5-di-tert-butylsalicylaldehyde. X-ray crystal structures of complexes 2, 3 and 5 reveal that they have a distorted octahedral geometry with the bonding parameters around the metal centres being practically similar. Stoichiometric oxygen atom transfer (OAT) properties of 5 with PPh3 were investigated using UV-Vis, 31P NMR and mass spectroscopy. In a CH2Cl2 solution, a dimeric Mo(V) complex [(µ-O){MoO(L5)}2](PF6)2 6 was formed while in methanol solution an air-sensitive Mo(IV) complex [MoO(OCH3)(L5)] 7 was obtained. The solid-state structure of the µ-oxo bridged dimer 6 was determined by X-ray diffraction. Complex 7 is unstable under ambient conditions and capable of reducing DMSO, thus showing reactivity analogous to that of DMSO reductases. Similarly, the OAT reactions of complexes 2-4 also resulted in the formation of dimeric Mo(V) and unsaturated monomeric Mo(IV) complexes that are analogous to complexes 6 and 7. Catalytic OAT at 25 °C could also be observed, using complexes 1-5 as catalysts for oxidation of PPh3 in deuterated dimethylsulfoxide (DMSO-d6), which functioned both as a solvent and oxidant. All complexes were also tested as catalysts for sulfoxidation of methyl-p-tolylsulfide and epoxidation of various alkene substrates with tert-butyl hydroperoxide (TBHP) as an oxidant. Complex 1 did not exhibit any sulfoxidation activity under the conditions used, while 2-5 catalyzed the sulfoxidation of methyl-p-tolylsulfide. Only complexes 2 and 3, with ligands containing halide substituents exhibited good to moderate activity for epoxidation of all alkene substrates studied, and, in general, good activity for all molybdenum(VI) catalysts was only exhibited when cis-cyclooctene was used as a substrate. No complex catalysed epoxidation of cis-cyclooctene when an aqueous solution of H2O2 was used as potential oxidant.en
dc.format.mimetypeapplication/pdf
dc.language.isoeng
dc.publisherElsevier
dc.relation.ispartofseriesPolyhedron
dc.rightsCC BY-NC-ND 4.0
dc.subject.othermolybdenum
dc.subject.othertripodal tetradentate ligand
dc.subject.otherepoxidation
dc.subject.otheroxygen atom transfer
dc.titleOxygen Atom Transfer Catalysis by Dioxidomolybdenum(VI) Complexes of Pyridyl Aminophenolate Ligands
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-202106023377
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineEpäorgaaninen ja analyyttinen kemiafi
dc.contributor.oppiaineEpäorgaaninen kemiafi
dc.contributor.oppiaineInorganic and Analytical Chemistryen
dc.contributor.oppiaineInorganic 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.volume205
dc.type.versionpublishedVersion
dc.rights.copyright© 2021 The Authors. Published by Elsevier Ltd
dc.rights.accesslevelopenAccessfi
dc.subject.ysomolybdeeni
dc.subject.ysokompleksiyhdisteet
dc.subject.ysokatalyytit
dc.format.contentfulltext
jyx.subject.urihttp://www.yso.fi/onto/yso/p11107
jyx.subject.urihttp://www.yso.fi/onto/yso/p30190
jyx.subject.urihttp://www.yso.fi/onto/yso/p15480
dc.rights.urlhttps://creativecommons.org/licenses/by-nc-nd/4.0/
dc.relation.doi10.1016/j.poly.2021.115234
jyx.fundinginformationWe gratefully acknowledge financial support from the COST Action CM1003 Biological oxidation reactions-mechanisms and design of new catalysts. MGR thanks the Robert A. Welch Foundation (Grant B-1093) for funding. The DFT calculations were performed at UNT through CASCaM, which is an NSF-supported facility (CHE-1531468). M.K.H. thanks the European Commission for an Erasmus Mundus predoctoral scholarship and Dr. Arun Kumar Raha for experimental assistance.
dc.type.okmA1


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