Cobalt and Iron Cyano Benzene Bis(Dithiolene) Complexes

New iron and cobalt bis(dithiolene) complexes [M(3cbdt)2] (3cbdt = 3-cyanobenzene-1,2-dithiolate) were prepared as tetraphenylphosphonium (Ph4P+) salts for Fe in the monoanionic state and for Co in both the dianionic and monoanionic states: (Ph4P)2[Fe(III)(3cbdt)2]2 (1); (Ph4P)2[Co(III)(3cbdt)2]2 (2...

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Published in:Crystals (Basel) Vol. 14; no. 5; p. 469
Main Authors: Costa, António G., Lopes, Gonçalo, Rodrigues, João F. G., Santos, Isabel C., Simão, Dulce, Lopes, Elsa B., Pereira, Laura C. J., Le Breton, Nolwenn, Choua, Sylvie, Baudron, Stéphane A., Almeida, Manuel, Rabaça, Sandra
Format: Journal Article
Language:English
Published: Basel MDPI AG 01.05.2024
MDPI
Subjects:
Analysis
Antiferromagnetism
Benzene
bis(dithiolene) metal transition complexes
Chemical Sciences
Cobalt
Coordination
Coordination chemistry
Cristallography
crystal structure
cyclic voltammetry
Diffraction
Geometry
Hydrocarbons
Hyperfine structure
Iron
Ligands
Magnetic permeability
Magnetic properties
Metals
Oxidation
Single crystals
Temperature dependence
thio-azo ligands
Transition metal compounds
Transition metals
Unit cell
Voltammetry
X-rays
magnetic properties
thio-azo ligands
cyclic voltammetry
electron paramagnetic resonance
crystal structure
iron
bis(dithiolene) metal transition complexes
cobalt
ISSN:2073-4352, 2073-4352
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Summary:New iron and cobalt bis(dithiolene) complexes [M(3cbdt)2] (3cbdt = 3-cyanobenzene-1,2-dithiolate) were prepared as tetraphenylphosphonium (Ph4P+) salts for Fe in the monoanionic state and for Co in both the dianionic and monoanionic states: (Ph4P)2[Fe(III)(3cbdt)2]2 (1); (Ph4P)2[Co(III)(3cbdt)2]2 (2); (Ph4P)2[Co(II)(3cbdt)2] (3). These compounds were characterized by single-crystal X-ray diffraction, cyclic voltammetry, EPR, and static magnetic susceptibility. Their properties are discussed in comparison with the corresponding complexes based on the isomer ligand 4-cyanobenzene-1,2-dithiolate (4cbdt) and 4,5-cyanobenzene-1,2-dithiolate (dcbdt), previously described by us. The Fe(III) and the Co(III) compounds (1 and 2) are isostructural, crystallizing in the triclinic P1¯ space group, with cis [M(III)(3cbdt)2] complexes dimerized in a trans fashion, and the transition metal (M = Fe, Co) has a distorted 4+1 square pyramidal coordination geometry. The Co(II) compound (3) crystallizes in the triclinic P1¯ space group, with the unit cell containing one cis and three trans inequivalent [Co(II)(3cbdt)2] complexes with the transition metal (Co) and having a square planar coordination geometry. The Fe(III) complex (1) is EPR-silent, and the static magnetic susceptibility shows a temperature dependence typical of dimers of antiferromagnetically coupled S = 3/2 spins with −J/kB = 233.6 K and g = 1.8. Static magnetic susceptibility measurements of compound (3) show that this Co(II) complex is paramagnetic, corresponding to an S = ½ state with g = 2, in agreement with EPR spectra showing in solid state a hyperfine structure typical of the I(59Co) = 7/2. Static susceptibility measurements of Co(III) complex (2) showed an increase in the paramagnetic susceptibility upon warming above 100 K, which is consistent with strong AFM coupling between dimerized S = 1 units with a constant −J/kB ~1286 K.
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ISSN:2073-4352
2073-4352
DOI:10.3390/cryst14050469