Iron(II) Tris-[N-4-substituted-3,5-di(2-pyridyl)-1,2,4-triazole] Complexes: Structural, Magnetic, NMR, and Density Functional Theory Studies

Show simple item record Kitchen, JA en White, NG en Boyd, Maruta en Moubaraki, B en Murray, KS en Boyd, Peter en Brooker, S en 2011-09-06T02:00:40Z en 2009-07-20 en
dc.identifier.citation INORG CHEM 48(14):6670-6679 20 Jul 2009 en
dc.identifier.issn 0020-1669 en
dc.identifier.uri en
dc.description.abstract Eight mononuclear iron(II) complexes of N-4-3,5-di(2-pyridyl)-1,2,4-triazole (Rdpt) ligands have been prepared and characterized. In all cases the iron(II)/ligand ratio used is 1:3, giving red complexes of the general formula [Fe-II(RdPt)(3)]-(BF4)(2) center dot solvents, in 55-89% yield. The ligands differ only in the nature of the N-4-substituent (amino, pyrrolyl, iso-butyl, methyl, phenyl, para-tolyl, 3,5-dichlorophenyl, and 4-pyridyl; for ligands adpt, pldpt, ibdpt, medpt, phdpt, ptdpt, Cldpt, and pydpt, respectively) allowing substituent effects on the properties of the resulting iron(II) complexes to be probed. The low temperature crystal structures of seven of the complexes reveal low spin iron(II) environments. Packing analyses reveal anion-pi and acetonitrile-pi interactions involving the tetrafluoroborate counteranions and interstitial acetonitrile molecules, respectively. Both "pi-pockets" and "pi-sandwiches" are observed. Solid state magnetic susceptibility measurements (4-300 K) indicate the iron(II) is low spin (LS) in all complexes at all temperatures studied, except for [Fe-II(pldpt)(3)](BF4)2 center dot 1(1)/2H(2)O which has the beginnings of spin crossover (SCO) at elevated temperatures. Downfield shifts and peak broadening observed in the variable temperature H-1 NMR studies indicate that in d(3)-nitromethane solution the LS [Fe-II(RdPt)(3))(2+) complexes are in equilibrium with a trace of a high spin (HS) species. N-15 NMR spectra (measured and calculated) of the ligands reveal that altering the N-4-substituent changes the chemical shift of the N-1 triazole and pyridine nitrogen atoms, allowing probing of the relationship between ligand substituent and the nature of the coordinating nitrogen atoms. en
dc.language EN en
dc.publisher AMER CHEMICAL SOC en
dc.relation.ispartofseries Inorganic Chemistry en
dc.rights Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. Previously published items are made available in accordance with the copyright policy of the publisher. Details obtained from en
dc.rights.uri en
dc.subject SPIN-CROSSOVER en
dc.subject DINUCLEAR COBALT(II) en
dc.subject ANION-BINDING en
dc.subject MONONUCLEAR en
dc.subject CHEMISTRY en
dc.subject 4-ISOBUTYL-3,5-DI(2-PYRIDYL)-4H-1,2,4-TRIAZOLE en
dc.subject COPPER(II) en
dc.subject NICKEL(II) en
dc.title Iron(II) Tris-[N-4-substituted-3,5-di(2-pyridyl)-1,2,4-triazole] Complexes: Structural, Magnetic, NMR, and Density Functional Theory Studies en
dc.type Journal Article en
dc.identifier.doi 10.1021/ic900634t en
pubs.issue 14 en
pubs.begin-page 6670 en
pubs.volume 48 en
dc.rights.holder Copyright: 2009 American Chemical Society en
dc.identifier.pmid 19534510 en
pubs.end-page 6679 en
pubs.publication-status Published en
dc.rights.accessrights en
pubs.subtype Article en
pubs.elements-id 117558 en
pubs.record-created-at-source-date 2010-09-28 en
pubs.dimensions-id 19534510 en

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