2024-03-29T02:09:37Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1117502020-06-01T11:03:22Zcom_10261_31com_10261_3com_10261_52707com_10261_5col_10261_284col_10261_52708
DIGITAL.CSIC
author
García-Monforte, M. Ángeles
author
Ara, Irene
author
Martín, Antonio
author
Menjón, Babil
author
Tomás, Milagros
author
Alonso, Pablo J.
author
Arauzo, Ana B.
author
Martínez, Jesús I.
author
Rillo, Conrado
funder
Ministerio de Ciencia e Innovación (España)
funder
Ministerio de Economía y Competitividad (España)
funder
European Commission
funder
Gobierno de Aragón
2015-03-04T09:18:00Z
2015-03-04T09:18:00Z
2014
Inorganic Chemistry 53(23): 12384-12395 (2014)
http://hdl.handle.net/10261/111750
10.1021/ic501719y
http://dx.doi.org/10.13039/501100004837http://dx.doi.org/10.13039/501100003329http://dx.doi.org/10.13039/501100000780http://dx.doi.org/10.13039/501100010067
Homoleptic organocobalt(III) compounds with formula [NBu4][CoIII(C6X5)4] [X = F (3), Cl (4)] were obtained in reasonable yields by chemical oxidation of the corresponding divalent species [NBu4]2[CoII(C6X5)4] [X = F (1), Cl (2)]. The [CoIII(C6X5)4]-/[CoII(C6X5)4]2- couples are electrochemically related by quasi-reversible, one-electron exchange processes at moderate potential: E1/2 = -0.29 (X = F) and -0.36 V (X = Cl) versus saturated calomel electrode. The [CoIII(C6X5)4]- anions in salts 3 and 4 show an unusual square-planar geometry as established by single-crystal X-ray diffraction methods. According to their stereochemistry, these CoIII derivatives (d6) are paramagnetic non-Kramers systems with a large zero-field splitting contribution and no observable electron paramagnetic resonance (EPR) spectrum. The thermal dependence of their magnetic susceptibilities can be explained in terms of a spin-Hamiltonian formalism with S = 1 ground state (intermediate spin) and substantial spin-orbit contribution. The magnetic properties of the square-planar d7 parent species [NBu4]2[CoII(C6X5)4] were also thoroughly studied both at microscopic (EPR) and macroscopic levels (alternating current and direct current magnetization measurements). They behave as S = 1/2 (low spin) systems with mainly (dz2 )1 electron configuration and a certain degree of s-orbital admixture that has been quantified. The electronic structures of all four open-shell [Co(C6X5)4]q- compounds (q = 1, 2) accounting for their respective magnetic properties are based on a common orbital energy-level diagram.
eng
closedAccess
Homoleptic organocobalt(III) compounds with intermediate spin
artículo
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accesoRestringido.pdf.txt