SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF RUTHENIUM AND OSMIUM CARBONYL CLUSTERS CONTAINING 4,6-DIMETHYLPYRIMIDINE-2-THIONE

Os-3(CO)(10)(MeCN)(2) reacts with 4,6-dimethylpyrimidine-2-thione (dmp ymt) in CH2Cl2 at room temperature to give Os-3(CO)(10)(pH)(mu-dmpymt) (1) and Os-3(CO)(10)(mu-H)(mu-SH) (2). The corresponding reaction of Ru-3(CO)(10)(MeCN)(2) with dmpymt gives Ru-3(CO)(9)(mu-H)(mu(3)-eta(2) -dmpymt) (3), Ru-3(CO)(10)(mu-H)(mu-dmpymt) (4) and Ru-3(CO)(10)(mu-dm pymt)(2) (5). Cluster 4 is thermally unstable and converts to 3 readil y on standing. Clusters 1, 2, 3 and 5 are fully characterized by IR, H -1 NMR, MS and X-ray crystallography. Crystals of 1 are orthorhombic, space group Pnrna with unit-cell dimensions a=14.932(2), b=16.290(2), c=18.649(2) Angstrom. Crystals of 2 are triclinic, space group P (1) o ver bar, Z=4, with unit-cell dimensions a=9.163(1), b=14.123(3), c=14. 305(2) Angstrom, alpha=70.31(1), beta=89.32(1), gamma=76.60(1)degrees. Complex 3 crystallizes in the monoclinic space group P2(1)/c with a=7 .793(1), b=15.555(1), c=17.259(1) Angstrom, beta=93.79(1)degrees. Comp lex 5 is monoclinic, space group C2/c, with a=17.972(7), b=12.988(6), c=13.516(4) Angstrom, beta=111.57(3)degrees.