Homoleptic, sigma-bonded octahedral superelectrophilic metal carbonyl cations of iron(II), ruthenium(II), and osmium(II). Part 2: Syntheses and characterizations of [M(CO)(6)][BF(4)](2) (M = Fe, Ru, Os)

As the first examples of homoleptic, sigma-bonded superelectrophilic metal carbonyl cations with tetrafluoroborate BF(4)](-) as the counter anions three thermally stable salts of the composition M(CO)(6)]BF(4)](2) (M = Fe, Ru, Os) have been synthesized and extensively characterized by thermochemical, structural, and spectroscopic methods. A common synthetic route, the oxidative carbonylation of either Fe(CO)(5) (XeF(2) as the oxidizer) or M(3)(CO)(12) (M = Ru, Os) (F(2) as the oxidizer) in the conjugate Bronsted-Lewis superacid HF/BF(3), was employed. The thermal behavior of the three salts, studied by differential scanning calorimetry (DSC) and gas-phase IR spectroscopy of the decomposition products, has been compared to that of the corresponding SbF(6)](-) salts. The molecular structures of M(CO)(6)]BF(4)](2) (M = Fe, Os) were obtained by single-crystal X-ray diffraction at 100 K. X-ray powder diffraction data for M(CO)(6)]BF(4)](2) (M = Ru, Os) were obtained between 100 and 300 K in intervals of 50 K. All three salts are isostructural and crystallized in the tetragonal space group I4/m (No. 87). As for the corresponding M(CO)(6)]SbF(6)](2) salts (M = Fe, Ru, Os), similar unit cell parameters and vibrational fundamentals were also found for the three BF(4)](-) compounds. For the structurally characterized salts M(CO)(6)]BF(4)](2) (M = Fe, Os), very similar bond parameters for both cations and anions were found. Hence, the invariance of structural and spectroscopic properties of M(CO)(6)](2+) cations (M = Fe, Ru, Os) extended from the fluoroantimonates Sb(2)F(11)](-) and SbF(6)](-) as counteranions also to BF(4)](-).