With sterically hindered 1-naphthalenethiol ligand, the copper complex [α-C~1~0H~7SCu]~n reacted with CS~2, in the presence of Ph~3P, to give a product of CS~2 insertion into Cu－S bonds. The crystal structure of the product is [Ph~3P)~2Cu(α-C~1~0H~7SCS~2)]· CS~2(1), determined by the X-ray diffraction method. The mononuclear insertion product (1) reacted with mixed solvents CH~2Cl~2/CH~3OH to form orange crystals, the structure of which is (Ph~3P)~2Cu(α- C~1~0H~7S)~2Cu(PPh~3)(2). In the complex (1), the Cu atom is pseudotetrahedrally coordinated by two S atoms of the thioxanthate ligand (α-C~1~0H~7SCS~2^-) and two P atoms of Ph~3P. Compound (2) is a neutral dinuclear copper complex, in which the two S atoms of the 1- naphthalenethiol ligands bridge two Cu atoms to form a quadrilateral. The two Cu atoms have different coordination situation. Cu(1) is planar trigonally coordinated by two bridge S atoms and one P atom of Ph~3P; while Cu(2) is coordinated by two bridge S atoms and two P atoms of Ph~3P to form a distorted tetrahedron. Crystal data for complex (1): space group p-1, a=1.4200(3) nm, b=1.5072(3) nm, c=1. 1747(2) nm, α=108.09(3), β=112.73(3), γ=75.41(3)°, V=2.1791(7) nm^3, D~c=1.371 g·cm^3, Z=2, R=0.0430 for 7660 independent reflections. Crystal data for complex(2) : space group C2, a=2.0771(4) nm, b=1.6340(3) nm, c=1.8861(4) nm, β=104.40(3)°, V=6.200(2) nm^3, D~c=1.320 g·cm^3, Z=4, R=0.0794 for 5673 independent reflections.

Key words: TRIPHENYLPHOSPHINE, NAPHTHALENE P, THIOPHENOLS, COPPER COMPLEX, CARBON DISULFIDE, X-RAY DIFFRACTION ANALYSIS, CRYSTAL STRUCTURE, INSERTION REACTION