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Co/Fe(alpha-Alkyl-tpdt)(2) (x-): Alkyl-Substituted Cobalt and Iron Bis-dithiolenethiophenic Complexes
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Tetraphenylphosphonium salts of Co and Fe complexes with alkyl substituted, tert-butyl (tb) and isopropyl (dp), 2,3-thiophenedithiolate (α-tpdt) ligands, namely TPP[Co(α-tb-tpdt)2] (3), TPP2[Fe(α-tb-tpdt)2]2 (4a-b), TPP[Co(α-dp-tpdt)2] (5) and TPP[Fe(α-dp-tpdt)2] (6) were prepared and characterized by cyclic voltammetry, single crystal. X-ray diffraction, magnetic susceptibility measurements and 57Fe Mössbauer spectroscopy Compound 3 and 5 are isostructural with their Au and Ni analogues with a square-planar coordination geometry. Compound 4 presents two polymorphs (4a-b) both showing a Fe(III). The magnetic susceptibility of 3 and 5 show a behavior dominated by antiferromagnetic interactions, with room temperature magnetic moments of 3.40 μB and 3.36 μB, respectively, indicating that these square-planar Co(III) complexes assume an intermediate spin electronic configuration (S=1) as supported by multiconfigurational DFT calculations.
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SILVA, Rafaela a. l., SANTOS, Rodrigo, ANDRADE, Marta m., SANTOS, Isabel c., COUTINHO, Joana t., PEREIRA, Laura c. j., WAERENBORGH, Joao c., VIEIRA, Bruno j. c., CIRERA FERNÁNDEZ, Jordi, RUIZ SABÍN, Eliseo, ALMEIDA, Manuel, BELO, Dulce. Co/Fe(alpha-Alkyl-tpdt)(2) (x-): Alkyl-Substituted Cobalt and Iron Bis-dithiolenethiophenic Complexes. _Inorganic Chemistry_. 2020. Vol. 59, núm. 13, pàgs. 9261-9269. [consulta: 24 de gener de 2026]. ISSN: 0020-1669. [Disponible a: https://hdl.handle.net/2445/185004]