@article {1059,
	title = {Homoleptic, sigma-bonded octahedral [M(CO)(6)](2+) cations of iron(II), ruthenium(II), and osmium(II): Part 1: Syntheses, thermochemical and vibrational characterizations, and molecular structures as [Sb2F11](-) and [SbF6](-) salts. A comprehensive, compa},
	journal = {Inorganic Chemistry},
	volume = {44},
	number = {12},
	year = {2005},
	note = {ISI Document Delivery No.: 934LPTimes Cited: 5Cited Reference Count: 100},
	month = {Jun},
	pages = {4189-4205},
	type = {Article},
	abstract = {Homoleptic octahedral, superelectrophilic sigma-bonded metal carbonyl cations of the type [M(CO)(6)](2+) (M = Ru, Os) are generated in the Bronsted-Lewis conjugate superacid HF/SbF5 by reductive carbonylation Of M(SO3F)(3) (M = Ru, Os) or OsF6. Thermally stable salts form with either [Sb2F11](-) or [SbF6](-) as anion, just as for the previously reported [Fe(CO)(6)](2+) cation. The latter salts are generated by oxidative (XeF2) carbonylation of Fe(CO)(5) in HF/ SbF5. A rationale for the two diverging synthetic approaches is provided. The thermal stabilities Of [M(CO)(6)][SbF6](2) salts, studied by DSC, range from 180 degrees C for M = Fe to 350 degrees C for M = Os before decarbonylation occurs. The two triads [M(CO)(6)][SbF6](2) and [M(CO)(6)][Sb2F11](2) (M = Fe, Ru, Os) are extensively characterized by single-crystal X-ray diffraction and vibrational and C-13 NMR spectroscopy, aided by computational studies of the cations. The three [M(CO)(6)][SbF6](2) salts (M = Fe, Ru, Os) crystallize in the tetragonal space group P4/mnc (No. 128), whereas the corresponding [Sb2F11](-) salts are monoclinic, crystallizing in space group P2(1)/n (No. 14). In both triads, the unit cell parameters are nearly invariant of the metal. Bond parameters for the anions [SbF6](-) and [Sb2F11](-) and their vibrational properties in the two triads are completely identical. In all six salts, the structural and vibrational properties of the [M(CO)(6)](2+) cations (M = Fe, Ru, Os) are independent of the counteranion and for the most part independent of M and nearly identical. Interionic C center dot center dot center dot F contacts are similarly weak in all six salts. Metal dependency is noted only in the C-13 NMR spectra, in the skeletal M-C vibrations, and to a much smaller extent in some of the C-O stretching fundamentals (A(1g) and T-1u). The findings reported here are unprecedented among metal carbonyl cations and their salts.},
	keywords = {ANTIMONY PENTAFLUORIDE, CRYSTAL-STRUCTURE, ELECTRON-DIFFRACTION, HEXAKIS(CARBONYL)IRON(II), INFRARED SPECTRA, MAS-NMR-SPECTRA, METAL-CARBONYL CATIONS, PHASE, SOLVENT SYSTEM, SUPERACID MEDIA, UNDECAFLUORODIANTIMONATE(V), WEAKLY COORDINATING ANIONS},
	isbn = {0020-1669},
	url = {<Go to ISI>://000229710600021},
	author = {Bernhardt, E. and Bach, C. and Bley, B. and Wartchow, R. and Westphal, U. and Sham, I. H. T. and von Ahsen, B. and Wang, C. Q. and Willner, H. and Thompson, R. C. and Aubke, F.}
}
@article {1059,
	title = {Homoleptic, sigma-bonded octahedral [M(CO)(6)](2+) cations of iron(II), ruthenium(II), and osmium(II): Part 1: Syntheses, thermochemical and vibrational characterizations, and molecular structures as [Sb2F11](-) and [SbF6](-) salts. A comprehensive, compa},
	journal = {Inorganic Chemistry},
	volume = {44},
	number = {12},
	year = {2005},
	note = {ISI Document Delivery No.: 934LPTimes Cited: 5Cited Reference Count: 100},
	month = {Jun},
	pages = {4189-4205},
	type = {Article},
	abstract = {Homoleptic octahedral, superelectrophilic sigma-bonded metal carbonyl cations of the type [M(CO)(6)](2+) (M = Ru, Os) are generated in the Bronsted-Lewis conjugate superacid HF/SbF5 by reductive carbonylation Of M(SO3F)(3) (M = Ru, Os) or OsF6. Thermally stable salts form with either [Sb2F11](-) or [SbF6](-) as anion, just as for the previously reported [Fe(CO)(6)](2+) cation. The latter salts are generated by oxidative (XeF2) carbonylation of Fe(CO)(5) in HF/ SbF5. A rationale for the two diverging synthetic approaches is provided. The thermal stabilities Of [M(CO)(6)][SbF6](2) salts, studied by DSC, range from 180 degrees C for M = Fe to 350 degrees C for M = Os before decarbonylation occurs. The two triads [M(CO)(6)][SbF6](2) and [M(CO)(6)][Sb2F11](2) (M = Fe, Ru, Os) are extensively characterized by single-crystal X-ray diffraction and vibrational and C-13 NMR spectroscopy, aided by computational studies of the cations. The three [M(CO)(6)][SbF6](2) salts (M = Fe, Ru, Os) crystallize in the tetragonal space group P4/mnc (No. 128), whereas the corresponding [Sb2F11](-) salts are monoclinic, crystallizing in space group P2(1)/n (No. 14). In both triads, the unit cell parameters are nearly invariant of the metal. Bond parameters for the anions [SbF6](-) and [Sb2F11](-) and their vibrational properties in the two triads are completely identical. In all six salts, the structural and vibrational properties of the [M(CO)(6)](2+) cations (M = Fe, Ru, Os) are independent of the counteranion and for the most part independent of M and nearly identical. Interionic C center dot center dot center dot F contacts are similarly weak in all six salts. Metal dependency is noted only in the C-13 NMR spectra, in the skeletal M-C vibrations, and to a much smaller extent in some of the C-O stretching fundamentals (A(1g) and T-1u). The findings reported here are unprecedented among metal carbonyl cations and their salts.},
	keywords = {ANTIMONY PENTAFLUORIDE, CRYSTAL-STRUCTURE, ELECTRON-DIFFRACTION, HEXAKIS(CARBONYL)IRON(II), INFRARED SPECTRA, MAS-NMR-SPECTRA, METAL-CARBONYL CATIONS, PHASE, SOLVENT SYSTEM, SUPERACID MEDIA, UNDECAFLUORODIANTIMONATE(V), WEAKLY COORDINATING ANIONS},
	isbn = {0020-1669},
	url = {<Go to ISI>://000229710600021},
	author = {Bernhardt, E. and Bach, C. and Bley, B. and Wartchow, R. and Westphal, U. and Sham, I. H. T. and von Ahsen, B. and Wang, C. Q. and Willner, H. and Thompson, R. C. and Aubke, F.}
}
@article {1110,
	title = {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)][BF4](2) (M = Fe, Ru, Os)},
	journal = {Inorganic Chemistry},
	volume = {44},
	number = {12},
	year = {2005},
	note = {ISI Document Delivery No.: 934LPTimes Cited: 8Cited Reference Count: 51},
	month = {Jun},
	pages = {4206-4214},
	type = {Article},
	abstract = {As the first examples of homoleptic, sigma-bonded superelectrophilic metal carbonyl cations with tetrafluoroborate [BF4](-) as the counter anions three thermally stable salts of the composition [M(CO)(6)][BF4](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) (XeF2 as the oxidizer) or M-3(CO)(12) (M = Ru, Os) (F-2 as the oxidizer) in the conjugate Bronsted-Lewis superacid HF/BF3, 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 [SbF6](-) salts. The molecular structures Of [M(CO)(6)][BF4](2) (M = Fe, Os) were obtained by single-crystal X-ray diffraction at 100 K. X-ray powder diffraction data for [M(CO)(6)][BF4](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)][SbF6](2) salts (M = Fe, Flu, Os), similar unit cell parameters and vibrational fundamentals were also found for the three [BF4](-) compounds. For the structurally characterized salts [M(CO)(6)][BF4](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 [Sb2F11](-) and [SbF6](-) as counteranions also to [BF4](-).},
	keywords = {ANTIMONY PENTAFLUORIDE, CHEMISTRY, GAS-PHASE, LEWIS-ACIDS, MAS-NMR-SPECTRA, MOLECULAR-STRUCTURE, SPECTROSCOPIC PROPERTIES, SYSTEM, UNDECAFLUORODIANTIMONATE(V), VIBRATIONAL-SPECTRA},
	isbn = {0020-1669},
	url = {<Go to ISI>://000229710600022},
	author = {Finze, M. and Bernhardt, E. and Willner, H. and Lehmann, C. W. and Aubke, F.}
}
@article {425,
	title = {A F-19 nuclear magnetic resonance study of the conjugate Bronsted-Lewis superacid HSO3F-SbF5. Part II},
	journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie},
	volume = {80},
	number = {9},
	year = {2002},
	note = {ISI Document Delivery No.: 607YFTimes Cited: 4Cited Reference Count: 31},
	month = {Sep},
	pages = {1265-1277},
	type = {Article},
	abstract = {Solutions of SbF5 in HSO3F with x(SbF5) = 0.012 to 0.405 are studied by 500 MHz H-1 NMR (299 K) and 471 MHz F-19 NMR (213-250 K), using NMR tubes fitted with fluoropolymer lining. The initial process during dissolution is the fast solvolysis of monomeric SbF5 in HSO3F according to SbF5 + nHSO(3)F left arrow SbF5 - n(SO3F)(n) + nHF (n = 1, 2). All HF formed during solvolysis will no longer be removed by reaction with glass, but will remain in the superacid system. Besides participation in the fast formation of various fluoro-fluorosulfato anions [SbF6 - n(SO3F)(n)](-) (n = 0, 1, 2) and acidium ions [H2X](+)((solv.)) (X= F, SO3F), HF is involved in slow-exchange reactions of the type [SbF6 - n(SO3F)(n)](-)((solv.)) + HF left arrow [SbF7 - n(SO3F)(n- 1)](-)((solv.)) + HSO3F (n = 1, 2) detected because of a delay of 3 months between sample preparation and measurements and confirmed by repeating theses measurements after a further 3 months. There are three notable differences to our earlier study, affecting concentrations of the fluoro-fluorosulfato antimonate anions observed: (i) in dilute solutions [SbF6](-) is formed in high concentrations (34.7-76.1\%), with [Sb2F11](-) now clearly detected at intermediate to high SbF5 concentrations (up to 5.8\%); (ii) bis-fluorosulfato anions (cis-, trans-[SbF4(SO3F)(2)](-)) are found in much lower concentrations only, which decrease further with time, while tris-fluorosulfato anions ([SbF3(SO3F)(3)](-)) are now no longer observed; (iii) these reduced concentrations of poly-fluorosulfato anions in dilute solutions are responsible for the formation of fewer mu-SO3F-oligomers at lower concentrations, when more SbF5 is added. As a consequence, the HSO3F-SbF5 magic acid system is now less complex than found previously and only seven anionic species are clearly observed.},
	keywords = {ANTIMONY PENTAFLUORIDE, antimony(V) fluoroanions, F-19 NMR, H-1 NMR, HF-SBF5, MEDIA, RELATIVE ACIDITY, SBF5, solvolysis, superacids, SYSTEMS},
	isbn = {0008-4042},
	url = {<Go to ISI>://000178817800011},
	author = {Kuhn-Velten, J. and Bodenbinder, M. and Brochler, R. and Hagele, G. and Aubke, F.}
}
@article {4713,
	title = {A F-19 nuclear magnetic resonance study of the conjugate Bronsted-Lewis superacid HSO3F-SbF5. Part 1},
	journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie},
	volume = {77},
	number = {11},
	year = {1999},
	note = {ISI Document Delivery No.: 253FETimes Cited: 5Cited Reference Count: 32},
	month = {Nov},
	pages = {1869-1886},
	type = {Article},
	abstract = {The Bronsted-Lewis superacid HSO3F-SbF5 or "magic acid" is re-investigated by modern F-19 NMR methods over a wide concentration range. The system is found to be considerably more complex than had been assumed previously. A,total of 13 different anions are identified of which only five have previously been identified in magic acid. With increasing SbF5 contents the concentration of monomeric anions like [SbF6](-), [SbF5(SO3F)](-), cis- and trans-[SbF4(SO3F)(2)](-), and mer-[SbF3(SO3F)(3)](-) gradually decreases. Except for [Sb2F11](-), which is present in very small concentrations only the formation of oligomers involves exclusively mu-fluorosulfato bridges. In addition to donor (SO3F)(-) and acceptor (SbF5) complex formation to give [SbF5(SO3F)](-) and possibly ligand redistribution, the solvolysis of SbF5 or SbF4(SO3F) in HSO3F appears to be the principal formation reaction for polyfluorosulfatofluoroantimonate(V) anions. In glass (NMR tubes) the solvolysis product HF is converted to the oxonium ion [H3O](+), which has previously been identified by H-1 NMR and structurally characterized as [H3O][Sb2F11] by us.},
	keywords = {ANTIMONY PENTAFLUORIDE, conjugate superacid, F-19 NMR spectra, FLUOROSULFATE, fluorosulfuric acid, HF-SBF5, magic acid, MEDIA, RELATIVE ACIDITY, SBF5, SYSTEMS},
	isbn = {0008-4042},
	url = {<Go to ISI>://000083545300020},
	author = {Zhang, D. L. and Heubes, M. and Hagele, G. and Aubke, F.}
}
