82585-02-2Relevant academic research and scientific papers
Chemistry of Et3P·CS2 metal complexes: Synthesis of 1,1-dithiolate complexes via nucleophilic attacks on [(triphos)Co(S2CPEt3)](BPh4)2. X-ray structure of [(triphos)Co(S2CO)]
Bianchini,Meli,Orlandini
, p. 4166 - 4169 (1982)
The synthesis of the 1,1-dithiolate cobalt(II) complexes [(triphos)Co(S2C(H)PEt3)]BPh4 (2), [(triphos)Co(S2CO)] (3), and [(triphos)Co(S2CS)] (4) (triphos = 1,1,1-tris((diphenylphosphino)methyl)ethane) via the reaction of complex [(triphos)Co(S2CPEt3)](BPh4)2 (1) with nucleophiles has been described. All the complexes have been characterized by appropriate physical methods. The molecular structure of 3 has been determined from counter diffraction data. Crystal data for 3: a = 20.294 (8) ?, b = 17.954 (7) ?, c = 10.218 (4) ?, orthorhombic, space group Pn21a, Z = 4. The stucture was refined by full-matrix least-squares techniques to R and Rw of 0.063 and 0.055, respectively. The cobalt atom is five-coordinated by the three phosphorus atoms of the triphos ligand and by the two sulfur atoms of the dithiocarbonate group in a distorted-square-pyramidal environment.
Reactivity of the triethylphosphine-carbon disulfide adduct (Et3P·CS2) toward cobalt(II) cations in the presence of the tris(tertiary phosphines) triphos and etriphos. X-ray crystal structure of the complex [(etriphos)Co(S2C(H)PEt3)](BPh4)2
Bianchini,Meli,Orlandini
, p. 4161 - 4165 (2008/10/08)
Depending on the reaction conditions, three different products, [(triphos)Co(S2CPEt3)](BPh4)2 (1), [(triphos) Co(S2C-(H)PEt3)](BPh4)2 (2), and [(triphos)Co(μ-CS2)Co(triphos)](BF4)2 (6), are obtained from the reaction of the triethylphosphine-carbon disulfide adduct Et3P·CS2 with cobalt(II) aquo cations in the presence of the tris(tertiary phosphine) 1,1,1-tris((diphenylphosphino)methyl)ethane, triphos. The substitution of the triphos with the etriphos ligand (etriphos = 1,1,1-tris((diethylphosphino)methyl)ethane) has helped us to clarify many aspects concerning both the structure and the formation mechanism of 2. The further reactivity of the complexes obtained toward reducing and oxidizing agents has been also probed. The X-ray structure determination of the cobalt(III) complex [(etriphos)Co(S2C(H)PEt3)](BPh4)2 (4), has been carried out from counter diffraction data. Crystal data for 4: a = 18.774 (8) A?, b = 25.094 (10) A?, c = 15.842 (7) A?, β = 114.2 (1)°, monoclinic, space group P21/n, Z = 4. The structure was refined by full-matrix least-squares techniques to R and Rw factors of 0.078 and 0.080, respectively. The metal atom is surrounded by the three phosphorus atoms of the etriphos ligand and by the two sulfur atoms of the S2C(H)PEt3 group in a distorted-square-pyramidal geometry.
