Homoleptic Organoderivatives of High‐Valent Nickel(III) |
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Authors: | Pablo J. Alonso Prof. Dr. Ana B. Arauzo Dr. María Angeles García‐Monforte Dr. Antonio Martín Dr. Babil Menjón Dr. Conrado Rillo Prof. Dr. Milagros Tomás Dr. |
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Affiliation: | 1. Instituto de Ciencia de Materiales de Aragón (I.C.M.A.), Universidad de Zaragoza‐C.S.I.C. C/Pedro Cerbuna 12, 50009 Zaragoza (Spain), Fax: (+34)?976‐761‐187;2. Servicio de Instrumentación Científica‐Medidas Físicas, Universidad de Zaragoza, C/Pedro Cerbuna 12, 50009 Zaragoza (Spain) |
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Abstract: | Homoleptic perhalophenyl derivatives of divalent nickel complexes with the general formula [NBu4]2[NiII (C6X5)4] [X=F ( 1 ), Cl ( 2 )] have been prepared by low‐temperature treatment of the halo‐complex precursor [NBu4]2[NiBr4] with the corresponding organolithium reagent LiC6X5. Compounds 1 and 2 are electrochemically related by reversible one‐electron exchange processes with the corresponding organometallate(III) compounds [NBu4][NiIII (C6X5)4] [X=F ( 3 ), Cl ( 4 )]. The potentials of the [NiIII (C6X5)4]?/[NiII (C6X5)4]2? couples are +0.07 and ?0.11 V for X=F or Cl, respectively. Compounds 3 and 4 have also been prepared and isolated in good yield by chemical oxidation of 1 or 2 with bromine or the amminium salt [N(C6H4Br‐4)3][SbCl6]. The [NiIII (C6X5)4]? species have SP‐4 structures in the salts 3 and 4 , as established by single‐crystal X‐ray diffraction methods. The [NiII (C6F5)4]2? ion in the parent compound 1 has also been found to exhibit a rather similar SP‐4 structure. According to their SP‐4 geometry, the NiIII compounds (d7) behave as S=1/2 systems both at microscopic (EPR) and macroscopic levels (ac and dc magnetization measurements). The spin Hamiltonian parameters obtained from the analysis of the magnetic behavior of 3 and 4 within the framework of ligand field theory show that the unpaired electron is centered mainly on the metal atom, with >97 % estimated d contribution. Thermal decomposition of 3 and 4 proceeds with formation of the corresponding C6X5? C6X5 coupling compounds. |
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Keywords: | electrochemistry EPR spectroscopy homoleptic compounds magnetic properties nickel |
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