Oxidative Addition of Halogens to Homoleptic Perfluoromethyl or Perfluorophenyl Derivatives of Platinum(II): A Comparative Study

Απλή σελίδα τεκμηρίου
dc.contributor.authorMenjon, B.en
dc.contributor.authorMartinez-Salvador, S.en
dc.contributor.authorGomez-Saso, M. A.en
dc.contributor.authorFornies, J.en
dc.contributor.authorFalvello, L. R.en
dc.contributor.authorMartin, A.en
dc.contributor.authorTsipis, A.en
dc.date.accessioned2015-11-24T16:43:42Z
dc.date.available2015-11-24T16:43:42Z
dc.identifier.issn0947-6539-
dc.identifier.urihttps://olympias.lib.uoi.gr/jspui/handle/123456789/8728
dc.rightsDefault Licence-
dc.subjectdensity functional calculationsen
dc.subjecthalogensen
dc.subjecthomoleptic compoundsen
dc.subjectoxidationen
dc.subjectplatinumen
dc.subjecttransition-metal-complexesen
dc.subjecth bond activationen
dc.subjectweakly coordinating anionsen
dc.subjectortho-perfluoroalkyl groupsen
dc.subjectdensity-functional theoryen
dc.subjectx-ray-structureen
dc.subjectreductive eliminationen
dc.subjectmolecular-structuresen
dc.subjectelectronic-structureen
dc.subjectfluorocarbon derivativesen
dc.titleOxidative Addition of Halogens to Homoleptic Perfluoromethyl or Perfluorophenyl Derivatives of Platinum(II): A Comparative Studyen
heal.abstractThe equilibrium geometries of the homoleptic perfluorinated organoplatinate(II) anions [Pt(CF(3))(4)](2-) and [Pt(C(6)F(5))(4)](2-) have been computed at the B3P86/LANL2DZ level of theory. Remarkably good agreement with the experimentally determined structures has been obtained by X-ray diffraction methods. The reactivity of [NBu(4)](2)[Pt(CF(3))(4)] (1) towards halogens (Cl(2), Br(2), and I(2)) has been investigated by using a combined experimental and theoretical approach. The perfluoromethyl derivative 1. has been found to undergo clean oxidative addition of the three halogens under investigation, giving rise to [NBu(4)](2)[trans-Pt(CF(3))(4)X(2)] (X = Cl (7), Br (10), I (13)) in a quantitative and stereoselective way. In the low-temperature reaction of the perfluorophenyl derivative [NBu(4)](2)[Pt(C(6)F(5))(4)] (3) with Cl(2) or Br(2), the corresponding oxidative-addition products [NBu(4)](2)[trans-Pt (C(6)F(5))(4)X(2)] (X = Cl (14), Br (15)) can also be obtained. In the case in which X = Br and working in CHCl(3) at -55 degrees C. it has been possible to detect the formation of an intermediate species to which we assign the formula [trans-Pt(C(6)F(5))(4)Br(ClCHCl(2))](-) (16). The solvento complex 16 is thermally unstable and prone to undergo reductive elimination Of C(6)F(5)-C(6)F(5). In the presence of PhCN, complex [NBu(4)][trans-Pt(C(6)F(5))(4)Br(NCPh)] (17) was isolated and structurally characterized. The reaction of 3 with I(2) gave no organoplatinum(IV) compound. Our comparative study reveals that the CF(3) group is especially suited to stabilize organometallic compounds in high oxidation states. This ability can be attributed to a combination of factors: its hardness, its high group electronegativity, its small size, and its reluctance to undergo reductive elimination processes.en
heal.accesscampus-
heal.fullTextAvailabilityTRUE-
heal.identifier.primaryDOI 10.1002/chem.200900323-
heal.identifier.secondary<Go to ISI>://000267721500010-
heal.identifier.secondaryhttp://onlinelibrary.wiley.com/store/10.1002/chem.200900323/asset/6371_ftp.pdf?v=1&t=h0f90b2u&s=2b8176d689de41ab5c46b1e783025f7a8bb170c1-
heal.journalNameChemistry-a European Journalen
heal.journalTypepeer reviewed-
heal.languageen-
heal.publicationDate2009-
heal.recordProviderΠανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείαςel
heal.typejournalArticle-
heal.type.elΆρθρο Περιοδικούel
heal.type.enJournal articleen

Αρχεία

Φάκελος/Πακέτο αδειών

Προβολή: 1 - 1 of 1
Μικρογραφία εικόνας
Ονομα:
license.txt
Μέγεθος:
1.74 KB
Μορφότυπο:
Item-specific license agreed upon to submission
Περιγραφή:
Κατεβάστε

Συλλογές

Άρθρα σε επιστημονικά περιοδικά ( Ανοικτά). ΧΗΜ