The compound [CoII{HN(OPPh2)(SPPh2)-O}2I2] (1) was synthesised by the reaction of cobalt in powder with the iodine adduct of tetraphenylthiooxoimidodiphosphinic acid, HN(OPPh2)(SPPh2), in Et2O; treatment of compound 1 with NaOH resulted in deprotonation of the ligands bound to the metal ion and a separation of [CoII{N(OPPh2)(SPPh2)-O,S}2](2). Molecular structures of complexes 1 and 2 were elucidated by X-ray diffraction analysis, which revealed a CoI2O2 tetrahedral core for compound 1 in which two neutral ligands bind through the oxygen atoms the CoII ion, and a tetrahedral CoO2S2 core for compound 2 with the oxygen and sulfur atoms of each anionic ligand chelating a CoII centre. Variable-temperature magnetic susceptibility measurements areconsistent with tetrahedral high-spin (S = 3/2) CoII that possessesa 4A2 ground state with best fit parameters g = 2.25, |D| = 12.0 cm–1 and g = 2.37, |D| = 11.9 cm–1 for complexes 1and 2, respectively. The compounds were further characterised by UV/Vis and IR spectroscopy. DFT calculations were performed on model complexes [CoII{N(OPH2)(SPH2)-O,S}2] (3) and [CoII{N(SPH2)2-S,S }2] (4) to compare the electronic properties of the CoO2S2 and CoS4 cores.
Tetrahedral CoII Complexes with CoI2O2 and CoO2S2 Cores – Crystal Structures of [Co{HN(OPPh2)(SPPh2)-O}2I2] and [Co{N(OPPh2)(SPPh2)-O,S}2] / M.C. Aragoni, M. Arca, M.B. Carrea, A. Garau, F.A. Devillanova, F. Isaia, V. Lippolis, G.L. Abbati, F. Demartin, C. Silvestru, S. Demeshko, F. Meyer. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - :29(2007), pp. 4607-4614.
Tetrahedral CoII Complexes with CoI2O2 and CoO2S2 Cores – Crystal Structures of [Co{HN(OPPh2)(SPPh2)-O}2I2] and [Co{N(OPPh2)(SPPh2)-O,S}2]
F. Demartin;
2007
Abstract
The compound [CoII{HN(OPPh2)(SPPh2)-O}2I2] (1) was synthesised by the reaction of cobalt in powder with the iodine adduct of tetraphenylthiooxoimidodiphosphinic acid, HN(OPPh2)(SPPh2), in Et2O; treatment of compound 1 with NaOH resulted in deprotonation of the ligands bound to the metal ion and a separation of [CoII{N(OPPh2)(SPPh2)-O,S}2](2). Molecular structures of complexes 1 and 2 were elucidated by X-ray diffraction analysis, which revealed a CoI2O2 tetrahedral core for compound 1 in which two neutral ligands bind through the oxygen atoms the CoII ion, and a tetrahedral CoO2S2 core for compound 2 with the oxygen and sulfur atoms of each anionic ligand chelating a CoII centre. Variable-temperature magnetic susceptibility measurements areconsistent with tetrahedral high-spin (S = 3/2) CoII that possessesa 4A2 ground state with best fit parameters g = 2.25, |D| = 12.0 cm–1 and g = 2.37, |D| = 11.9 cm–1 for complexes 1and 2, respectively. The compounds were further characterised by UV/Vis and IR spectroscopy. DFT calculations were performed on model complexes [CoII{N(OPH2)(SPH2)-O,S}2] (3) and [CoII{N(SPH2)2-S,S }2] (4) to compare the electronic properties of the CoO2S2 and CoS4 cores.Pubblicazioni consigliate
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