Synthesis and structural characterization of ruthenium and osmium carbonyl clusters containing 4,6-dimethylpyrimidine-2-thione

Abstract

Os3(CO)10(MeCN)2 reacts with 4,6-dimethylpyrimidine-2-thione (dmpymt) in CH2CI2 at room temperature to give Os3(CO)10(μ-H)(μ-dmpymt) (1) and Os3(CO)10(μ-H)(μ-SH) (2). The corresponding reaction of Ru3(CO)10(MeCN)2 with dmpymt gives Ru3(CO)9(μ-H)(μ3-ν2-dmpymt) (3), Ru3(CO)10(μ-H)(μ-dmpymt) (4) and Ru3(CO)10(μ-dmpymt)2 (5). Cluster 4 is thermally unstable and converts to 3 readily on standing. Clusters 1, 2, 3 and 5 are fully characterized by IR, 1H NMR, MS and X-ray crystallography. Crystals of 1 are orthorhombic, space group Pnma with unit-cell dimensions a = 14.932(2), b = 16.290(2), c = 18.649(2) A ̊. Crystals of 2 are triclinic, space group P1, Z = 4, with unit-cell dimensions a = 9.163(1), b = 14.123(3), c =14.305(2) A ̊, α = 70.31(1), β = 89.32(1), γ = 76.60(1)°. Complex 3 crystallizes in the monoclinic space group P21/c with a = 7.793(1), b = 15.558(1), c = 17.259(1) A ̊, β = 93.79(1)°. Complex 5 is monoclinic, space group C2/c, with a = 17.972(7), b = 12.988(6), c = 13.516(4) A ̊, β = 111.57(3)°. © 1995.