Abstract: The reactions of carbonyl ruthenium Ru₃(CO)₁₂ with two cyclic dithiophosphinate SP(C₆H₄OR)(S)N(C₆H₅)N C(Me)(R=Me, Et) yields four novel dinuclear and trinuclear ruthenium carbonyl clusters with P, S-containing lignads Ru₃(CO)₈(μ₃-S)₂ [ P (C₆H₄OR)N(C₆H₅)NC(Me)S](1; R=Me; 3; R=Et) and Ru₂(CO)₆ [μ-η₂-P(C₆H₄OR)N(C₆H₅)NC(Me)S](2; R=Me; 4; R=Et). These clusters were characterized by elementary analysis, IR, ¹H NMR and MS spectroscopy. The crystal structures of clusters 1 and 2 were determined by X-ray diffraction techniques. The crystal of cluster 1 belongs to triclinic system with space group P1, a=1.075 5(2) nm, b=1.576 0(2) nm, c=0.907 8(1) nm, α= 98.12(7)°, β=96.64(4)°, γ=79.67(5)°, V=1.492 1(4) nm³, Z=2, R(wR)=0.030 3(0.061 5). The molecule consists of a opened triangle of ruthenium atoms capped above and below the plane by sulphur. Ru₃(μ₃-S)₂ core is a distorted square pyramid geometry. The site of five-membered hetero cyclic phosphine substitution is equatorial to the tri-ruthenium plane and is at an axial site of Ru1. The crystal of cluster 2 belongs to monoclinic system with space group P2(1)/n, a= 1.124 3(4) nm, b=1.410 5(5) nm, c=1.629 45(7) nm, β=107.06(5)°, V=2.470 2(2) nm³, Z=4, R(wR)=0.024 8(0.044 1). The dinuclear cluster contains two six-membered chelate rings Ru1SCNNP and Ru2SCNNP, they enhance the stability of the cluster.

Key words: Carbonyl ruthenium cluster, P, S contained ligand, Synthesis, Crystal structure