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

Article abstract of DOI:10.1021/ic00142a011

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 R_w 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.