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

Abstract

Os 3(CO) 10(MeCN) 2 reacts with 4,6-dimethylpyrimidine-2-thione (dmpymt) in CH 2CI 2 at room temperature to give Os 3(CO) 10(μ-H)(μ-dmpymt) ( 1) and Os 3(CO) 10(μ-H)(μ-SH) ( 2). The corresponding reaction of Ru 3(CO) 10(MeCN) 2 with dmpymt gives Ru 3(CO) 9(μ-H)(μ 3-ν 2-dmpymt) ( 3), Ru 3(CO) 10(μ-H)(μ-dmpymt) ( 4) and Ru 3(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 P 1, 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 P2 1/ 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)° .