Electronic structure calculations on multiply charged anions containing M-S bonds (M = Cr, Mo, W) and their heterobimetallic cluster complexes

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dc.contributor.authorGili, P.en
dc.contributor.authorTsipis, A. C.en
dc.date.accessioned2015-11-24T16:57:41Z
dc.date.available2015-11-24T16:57:41Z
dc.identifier.issn0020-7608-
dc.identifier.urihttps://olympias.lib.uoi.gr/jspui/handle/123456789/10606
dc.rightsDefault Licence-
dc.subjectthiomolybdatesen
dc.subjectdinuclear clustersen
dc.subjecttrinuclear clustersen
dc.subjectdensity functional theoryen
dc.subjectvibrational frequenciesen
dc.subjectacid catalyzed formation reactionsen
dc.subjectdensity-functional theoryen
dc.subjectcrystal-structureen
dc.subjecttetraalkylammonium thiomolybdatesen
dc.subjectcorrelation-energyen
dc.subjectpossible relevanceen
dc.subjectgreen-functionen
dc.subjectactive-siteen
dc.subjectapproximationen
dc.subjectequilibriumen
dc.subjectammoniumen
dc.titleElectronic structure calculations on multiply charged anions containing M-S bonds (M = Cr, Mo, W) and their heterobimetallic cluster complexesen
heal.abstractMolecular and electronic structures of multiply charged mononuclear [CrS4](2-/3-), [MoOxS4-x](2-/3-) (x = 0-4) and [WS4](2-/3-) anionic species, and their heterobimetallic dinuclear and trinuclear clusters formulated as [MoOS3(CuCl)](2-), [WOS3(CuCl)](2-), [MoS4{Cu(CN)1](2-), [(CN)Cu(mu-CrS4)Cu(CN)](2-), [(CN)Cu(mu-MoS4)Cu(CN)](2-), [ClCu(mu-MoS4)CuCl](2-), [Cl2Fe(mu-MoS4)CUCl2](2-), and [(CN)Cu(mu-WS4)Cu(CN)](2-) have been investigated using electronic structure calculation (HF, MP4SDQ and DFT) methods. For the discrete mononuclear anions HF/lanl2dz(M)U631+G*(S,O) method provided the best description of their molecular structures, while for the heterobimetallic dinuclear and trinuclear clusters the B3LYP/lanl2dz(M)U631+G* method gave equilibrium geometries closely resembling the experimental ones. Electronic and spectroscopic (IR, UV-Vis) properties of the thiometalates are discussed in relation to their structures, while the bonding mechanism was analyzed in the framework of the natural bond orbital (NBO) approach. The nature of the highest occupied molecular orbitals (HOMOs) of all thiometalates indicated their ability to act as ligands coordinated with metal centers and forming clusters of higher nuclearity. The lowest-lying vertical one-electron detachment processes from the ground state of the [CrS4](2/3-), [MoOxS4-x](2/3-) (x = 0-4) and [WS4](2/3-) anions have been calculated using the outer valence Green's function (OVGF) method. Interestingly, in the heterobimetallic dinuclear and trinuclear clusters intemetallic (MM)-M-...' interactions exist corresponding to d10 -> d(0) dative bonding. Finally, the complete energetic and geometric profile of the successive acid-catalyzed formation reactions: [MoO4](2-) HS- -> H+ [MoO3S](2-) HS- -> H+ [MoO2S2](2-) HS- -> H+ [MoOS3](2-) HS- -> H+ [MoS4](2-) and the reverse hydrolysis reactions have been delineated and details of the mechanism have been furnished. (c) 2006 Wiley Periodicals, Inc. Int J Quantum Chem 107: 418-439, 2007en
heal.accesscampus-
heal.fullTextAvailabilityTRUE-
heal.identifier.primaryDoi 10.1002/Qua.21087-
heal.identifier.secondary<Go to ISI>://000242652700021-
heal.identifier.secondaryhttp://onlinelibrary.wiley.com/store/10.1002/qua.21087/asset/21087_ftp.pdf?v=1&t=h0f8zmhw&s=acbb072ca49a253b70150e62547d5dedbeb506c9-
heal.journalNameInternational Journal of Quantum Chemistryen
heal.journalTypepeer reviewed-
heal.languageen-
heal.publicationDate2007-
heal.recordProviderΠανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείαςel
heal.typejournalArticle-
heal.type.elΆρθρο Περιοδικούel
heal.type.enJournal articleen

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