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Reaction of Os3(CO)12 with thionylaniline in refluxing methylcyclohexane results in Os3(CO)9(mu3-NPh)(mu3-S) (1) in good yield. Compound 1 and Os3(CO)9(mu3-eta2-(PhN)2SO)(mu3-S) (2) are produced when Os3(CO)10(NCMe)2 is treated with thionylaniline. Compound 1 reacts with trimethylamine oxide in the presence of acetonitrile to produce Os3(CO)8(NCMe)(mu3-NPh)(mu3-S) (3). Compounds 1-3 were characterized by mass, IR and NMR spectroscopies and their structures were determined by single-crystal X-ray diffraction.

Five ruthenium cluster complexes containing sulfido, phenylimido and (phenylimino)thio ligands were synthesized by reacting Ru3(CO)12 with the SO2 derivative N-sulfinylaniline, PhN==S==O, in refluxing toluene. The five, which were obtained in low yields, are Ru3(CO)9(mu3-NPh)(mu3-S), Ru3(CO)9(mu3-NPh)2, Ru4(CO)10(mu-CO)(mu4-eta2-SNPH)(mu4-S), and Ru4(CO)10(mu-CO)(mu4-eta2-SNPh)(mu4-NPh). They were characterized using mass, infrared and NMR spectroscopy.

The interaction of W(PhC triple bond CPh)3(CO) with diphenylacetylene promoted alkyne-alkyne coupling resulting in the production of a cyclobutadiene complex. Structural studies using 13C nuclear magnetic resonance spectroscopy were conducted on W(eta4-C4Ph4)(PhC triple bond CPh)2(CO) to determine the crystal properties of the complex. The electronic configuration and reactivity experiments also provided data regarding the geometry of the complexes.

Treatment of the open-cage fullerene C63H4NO2(Ph)2(Py)(N2C6H4) ( 1) with methanol at 150 °C results in an orifice-enlargement reaction to give C69H8NO(CO2Me)(Ph)(Py)(N2C6H4) ( 2). The overall yield from C60 to isolated 2 is 6.1 % (four steps). Compound 2 contains a 24-membered elliptic orifice that spans 8.45 Å along the major axis and 6.37 Å along the minor axis. The skeleton of 2 resembles the hypothetic C60H10 (5,5)-carbon nanotube endcap. The cup-shaped structure of 2 is able to include water, hydrogen cyanide, and acetylene, forming H2O@ 2, HCN@ 2, and C2H2@ 2, respectively. The molecular structures of H2O@ 2 and HCN@ 2 have been determined by X-ray crystallography. The 1H NMR spectra reveal substantial upfield shifts for the endohedral species, such as δ=−10.30 (for H2O), −2.74 and −14.26 (for C2H2), and −1.22 ppm (for HCN), owing to the strong shielding effects of the fullerene cage. [ABSTRACT FROM AUTHOR]

The reductive dimerization and thermal rearrangement of biphenylene coordinated to tricarbonylmanganese were investigated. Novel ((eta(super 6)-C12H8)Mn(CO)3)(super +)(BF4)(super -) (1(super +)BF4 (super -))(super 10) in 87% yield were described for this purpose. A diagram was presented in which each manganese atom is linked to three terminal carbonyls and a cyclopentadienyl ligand. The two benzopentalene units C7-C18 and C19-C30 are shown to be planar.

Analytically pure C60H18 is obtained by a Ru3 cluster complexation and decomplexation method. The crystal structure of C60H18 consists of one flattened hemisphere, to which all 18 hydrogen atoms are symmetrically bonded, and one curved hemisphere akin to C60. A benzenoid ring in the flattened hemisphere is isolated from the residual π systems by a belt composed of sp3-hybridized CH units. The average out-of-plane distances for carbon atoms attached to the benzenoid ring (0.14 Å) is substantially larger than that found in C60F18 (0.06 Å). Several long C(sp3)C(sp3) single bond lengths [1.61(3)-1.65(3) Å] are observed for C60H18. The reaction of [Ru3(CO)12] and C60H18 produces [Ru3(CO)9(μ3-η2,η2,η2-C60H18)] ( 1), where the Ru3 triangle is regiospecifically linked to the hexagon opposite to the benzenoid ring. Compound 1 is the first transition metal complex of a polyhydrofullerene (fullerane). C60H18 and 1 have been characterized by 1H and 13C NMR, UV/Vis, and mass spectroscopies. The HOMO-LUMO gap of C60H18 is evaluated to be 1.51 V by cyclic voltammetry. [ABSTRACT FROM AUTHOR]