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Zwitterionic Cobalt Complexes with Bis(diphenylphosphino)(N-thioether)amine Assembling Ligands: Structural, EPR, Magnetic, and Computational Studies.

hal.structure.identifierInstitut de Chimie de Strasbourg
dc.contributor.authorFLIEDEL, Christophe
hal.structure.identifierInstitut de Chimie de Strasbourg
dc.contributor.authorROSA, Vitor
hal.structure.identifierTGE Réseau National de RPE interdisciplinaire - 3443 [RENARD]
dc.contributor.authorVILENO, Bertrand
hal.structure.identifierInstitut de Chimie de Strasbourg
dc.contributor.authorPARIZEL, Nathalie
hal.structure.identifierInstitut de Chimie de Strasbourg
dc.contributor.authorCHOUA, Sylvie
hal.structure.identifierInstitut de Chimie de Strasbourg
dc.contributor.authorGOURLAOUEN, Christophe
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorROSA, Patrick
hal.structure.identifierInstitut de Chimie de Strasbourg
dc.contributor.authorTUREK, Philippe
hal.structure.identifierInstitut de Chimie de Strasbourg
dc.contributor.authorBRAUNSTEIN, Pierre
dc.date.issued2016
dc.identifier.issn0020-1669
dc.description.abstractEnThe coordination of two heterofunctional P,P,S ligands of the N-functionalized DPPA-type bearing an alkylthioether or arylthioether N-substituent, (Ph2P)2N(CH2)3SMe (1) and (Ph2P)2N(p-C6H4)SMe (2), respectively, toward cobalt dichloride was investigated to examine the influence of the linker between the PNP nitrogen and the S atoms. The complexes [CoCl2(1)]2 (3) and [CoCl2(2)]2 (4) have been isolated, and 3 was shown by X-ray diffraction to be a unique dinuclear, zwitterion containing one CoCl moiety bis-chelated by two ligands 1 and one CoCl3 fragment coordinated by the S atom of a thioether function. The FT-IR, UV-vis, and EPR spectroscopic features of 3 were analyzed as the superposition of those of constitutive fragments identified by a retrosynthetic-type analysis. A similar approach provided insight into the nature of 4 for which no X-ray diffraction data could be obtained. A comparison between the spectroscopic features of 4 and of its constitutive fragments, [CoCl(2)2]PF6 (7) and [H2']2[CoCl4] (8) (2' = NH2(p-C6H4)SMe), and between those of 4 and 3 suggested that 4 could either have a zwitterionic structure, similar to that of 3, or contain a tetrahedral dicationic bis-chelated Co center associated with a CoCl4 dianion. Magnetic and EPR studies and theoretical calculations were performed. Doublet spin states were found for the pentacoordinated complexes [CoCl(1)2]PF6 (5) and 7 and anisotropic quadruplet spin states for the tetrahedral complexes [CoCl3(H1')] (6) (1' = NH2(CH2)3SMe) and 8. A very similar behavior was observed for 3 and 4, consisting in the juxtaposition of noninteracting doublet and quadruplet spin states. Antiferromagnetic interactions explain the formation of dimers for 6 and of layers for 8. The EPR signatures of 3 and 4 correspond to the superposition of low-spin nuclei in 5 and 7 and high-spin nuclei in 6 and 8, respectively. From DFT calculations, the solid-state structure of 4 appears best described as zwitterionic, with a low-spin state for the Co1 atom.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enZwitterionic Cobalt Complexes with Bis(diphenylphosphino)(N-thioether)amine Assembling Ligands: Structural, EPR, Magnetic, and Computational Studies.
dc.typeArticle de revue
dc.identifier.doi10.1021/acs.inorgchem.5b02889
dc.subject.halChimie/Matériaux
bordeaux.journalInorganic Chemistry
bordeaux.page4183-4198
bordeaux.volume55
bordeaux.issue9
bordeaux.peerReviewedoui
hal.identifierhal-01315379
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01315379v1
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