The reaction of cobalt powder with iodine activated by tetraphenyldithioimidodiphosphorane (Ph2P(S)NHP(S)Ph2) (LH) gives the complex CoL2 (1). Its solid-state structure [tri-clinic, space group P1̄ (No. 2), Z = 2, a = 13.321(2) Å, b = 13.872(2) Å, c = 14.394(3) Å, α = 82.500(10)°, β = 65.950(10)°, γ = 69.640(10)°] comprises discrete, monomeric molecules where a CoII ion is coordinated to four sulphur atoms by two bidentate anionic ligands L in a distorted tetrahedral CoS4 core. The electrochemistry of LH · I2 and CoL2 has been studied by cyclic voltammetry. FT-IR, Raman, 31 P-NMR spectroscopies, are in accordance with the structural features of the complex. Hybrid-DFT calculations have been used to gain an insight on the π properties of LH and L.
Reaction of cobalt powder with iodine activated by tetraphenyldithioimidodiphosphorane (LH). Crystal structure of CoL2
M. Carla Aragoni;Massimiliano Arca;Alessandra Garau;Vito Lippolis;
2000-01-01
Abstract
The reaction of cobalt powder with iodine activated by tetraphenyldithioimidodiphosphorane (Ph2P(S)NHP(S)Ph2) (LH) gives the complex CoL2 (1). Its solid-state structure [tri-clinic, space group P1̄ (No. 2), Z = 2, a = 13.321(2) Å, b = 13.872(2) Å, c = 14.394(3) Å, α = 82.500(10)°, β = 65.950(10)°, γ = 69.640(10)°] comprises discrete, monomeric molecules where a CoII ion is coordinated to four sulphur atoms by two bidentate anionic ligands L in a distorted tetrahedral CoS4 core. The electrochemistry of LH · I2 and CoL2 has been studied by cyclic voltammetry. FT-IR, Raman, 31 P-NMR spectroscopies, are in accordance with the structural features of the complex. Hybrid-DFT calculations have been used to gain an insight on the π properties of LH and L.
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