Syntheses and Crystal Structures of Bis(dimethyldithiocarbamato)-(4,6-diphenyl-4,6-diphosphanonane-1,9-diammonium) cobalt(III) and Chloro(4,9-diphenyl-4,9-diphosphadodecane-1,12-diamine)nickel(II) Complexes

Article abstract of DOI:10.1246/bcsj.69.1947

The reaction of tetramethylthiuram disulfide with a methanol solution containing CoCl₂·6H₂O and 4,6-diphenyl-4,6-diphosphanonane-1,9-diamine (313NPPN) gave complexes of [Co(dtc)₂{rac(P)- or meso(P)-313HNPPNH}]³⁺ (313HNPPNH=diprotonated form of 313NPPN, dtc=dimethyldithiocarbamate ion). The crystal structure of the perchlorate salt of the meso(P) isomer was determined by X-ray analysis. Crystal data: monoclinic, P2₁/c, a=10.789(2), b=30.325(9), c=12.888(2) A, β=102.06(1)°, V=4123(1) A³, D_x=1.55 g cm^-3, Z=4, and R=0.077 for 3347 reflections. The 313HNPPNH ligand in the complex coordinates to the Co(III) center through two phosphorus atoms as a didentate four-membered chelate ligand. The crystal structure of [Co(dtc)₂{NH₂(CH₂)₃P(CH ₂OH)(C₆H₅)}]B(C₆H₅) ₄, which formed as a by-product in the preparation of the above Co(III)-313HNPPNH complexes, was also determined. Crystal data: triclinic, P1, a=13.817(2), b=15.277(3), c=10.737(2) A, α=109.90(1), β=94.14(2), γ=101.00(1)°, V=2068.8(7) A³, D_x=1.31 g cm^-3, Z=2, and R=0.053 for 4303 reflections. [NiCl{rac(P)-343NPPN}]PF₆ (343NPPN=4,9-diphenyl-4,9-diphosphadodecane-1,12-diamine) was prepared by the reaction of 343NPPN with NiCl₂·6H₂O, and the crystal structure was determined. Crystal data: monoclinic, P2₁/n, a=8.367(2), b=24.058(2), c=13.988(2) A, β=106.17(1)°, V=2704(1) A³, D_x=1.54 g cm^-3, Z=4, and R=0.053 for 3043 reflections. The geometry of the complex is a distorted square pyramid with a chloride ion at the apical position, and the 343NPPN ligand functions as a tetradentate chelate ligand.