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Synthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systems

2010-09-06Journal article Open access
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dc.contributor.authorWanke, Riccardo
dc.contributor.authorGuedes Da Silva, M. Fátima C.
dc.contributor.authorLancianesi, Stefano
dc.contributor.authorSilva, Telma F. S.
dc.contributor.authorMartins, Luisa
dc.contributor.authorPettinari, Claudio
dc.contributor.authorPombeiro, Armando
dc.date.accessioned2011-11-24T16:52:06Z
dc.date.available2011-11-24T16:52:06Z
dc.date.issued2010-09-06
dc.description.abstractThe new potentially N-4-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-ypethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe-II, Ni-II, Zn-II, Cu-II, Pd-II, and V-III centers has been studied. Reaction of (1) with Fe(BF4)(2)center dot 6H(2)O yields [Fe(TpmPy)(2)](BF4)(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn-II or Ni-II chlorides give the corresponding metal complexes with general formula [MCl2(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)Cl-2 (5)) or the pyridyl-side (for [ZnCl2(TpmPy)(2)] (4), [ZnCl2(TpmPy(Ph))(2)] (6) and [NiCl2(TpmPy(Ph))(2)] (7)). The reaction of (1) with VCl3 gives [VOCl2(TpmPy)] (8) that shows the N-3-pyrazolyl coordination-mode. Moreover, (1) and react with cis-[PdCl2(CH3CN)(2)] to give the disubstituted complexes [PdCl2(TprnPy)(2)] (9) and [PdCl2(TpmPy(Ph))(2)] (10), respectively, bearing the scorpionate coordinated via the pyridyl group. Compounds (9) and (10) react with Fe(BF4)(2) to give the heterobimetallic Pd/Fe systems [PdCl2(mu-TpmPy)(2)-Fe](BF4)(2) (11) and [PdCl2(mu-TpmPy(Ph))(2)Fe-2(H2O)(6)]BF4)(4) (13), respectively. Compound (11) can also be formed from reaction of (3) with cis-[PdCl2(CH3CN)(2)], while reaction of (3) with Cu(NO3)(2).2.5H(2)O generates [Fe(mu-TpmPy)(2)-Cu(NO3)(2)](BF4)(2) (12), confirming the multidentate ability of the new chelating ligands. The X-ray diffraction analyses of compounds (1), (3), (4), (5), and (9) are also reported.por
dc.identifier.citationWanke R, Silva M F C G, Lancianesi S, Silva T F S, Martins L M D R S, Pettinari C, Pombeirot A J L. Synthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systems.Inorganic Chemistry. 2010; 49 (17): 7941-7952.por
dc.identifier.issn0020-1669
dc.identifier.urihttp://hdl.handle.net/10400.21/557
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherAmer Chemical Socpor
dc.relation.ispartofseries17
dc.subjectSpin-state crossoverpor
dc.subjectTris(Pyrazolyl) methane ligandspor
dc.subjectPeroxidative oxidationpor
dc.subjectMolecular materialspor
dc.subjectInfrared spectrapor
dc.subjectAngular-overlappor
dc.subjectIron(II)por
dc.subjectPalladium(II)por
dc.subjectUnitspor
dc.subjectZincpor
dc.titleSynthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systemspor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.conferencePlaceWashingtonpor
oaire.citation.endPage7952por
oaire.citation.issue49por
oaire.citation.startPage7941por
oaire.citation.titleInorganic Chemistrypor
person.familyNameWanke
person.familyNameGuedes da Silva
person.familyNameMartins
person.familyNamePettinari
person.familyNamePombeiro
person.givenNameRiccardo
person.givenNameM. Fátima C.
person.givenNameLuisa
person.givenNameClaudio
person.givenNameArmando
person.identifier789079
person.identifier637885
person.identifier.ciencia-idE611-325F-1931
person.identifier.ciencia-id7619-8E8E-979A
person.identifier.ciencia-idE218-E297-A4EA
person.identifier.ciencia-id8311-38FA-CEFB
person.identifier.orcid0000-0002-5480-7905
person.identifier.orcid0000-0003-4836-2409
person.identifier.orcid0000-0002-5403-9352
person.identifier.orcid0000-0002-2547-7206
person.identifier.orcid0000-0001-8323-888X
person.identifier.ridH-8274-2012
person.identifier.ridG-6210-2011
person.identifier.ridI-5945-2012
person.identifier.scopus-author-id6701761571
person.identifier.scopus-author-id8650947800
person.identifier.scopus-author-id7006581579
person.identifier.scopus-author-id7006067269
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
relation.isAuthorOfPublication65993438-6a74-4b50-b047-3874069290eb
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relation.isAuthorOfPublication.latestForDiscovery8ed70b09-b4d3-4a5d-9f75-12b13a332204

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