@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 {771,
	title = {Predominantly sigma-bonded metal carbonyl cations (sigma-carbonyls): New synthetic, structural, and bonding concepts in metal carbonyl chemistry},
	journal = {Chemistry-a European Journal},
	volume = {9},
	number = {8},
	year = {2003},
	note = {ISI Document Delivery No.: 669ZKTimes Cited: 7Cited Reference Count: 60},
	month = {Apr},
	pages = {1668-1676},
	type = {Article},
	abstract = {Predominantly sigma-bonded metal carbonyl cations (sigma-carbonyls) are conveniently generated in the Lewis superacid SbF5 or the conjugate Bronsted-Lewis superacid HF-SbF5, primarily by solvolytic or reductive carbonylations. Thermally stable salts are formed with the fluoroantimonate(v) ions [SbF6](-) and [Sb2F11](-). The salts are characterised by analytical, structural, spectroscopic and computational methods. Most homoleptic carbonyl cations have very regular geometries, comensurate with their d-electron configurations: linear (d(10)), square planar (d(8)) or octahedral(d(6)). The cations with metals in oxidation states of +2 or +3 are termed "superelectrophilic". Extended molecular structures form by significant interionic C-F contacts with electrophilic carbon as acceptor. To account for all experimental observations, a conceptually simple synergetic bonding model is proposed. An outlook at anticipated future developments based on very recent results is provided.},
	keywords = {<PT(CO)(4)><SB2F11>(2), carbonyl ligands, CATIONS, COMPLEXES, CRYSTAL, fluoro antimonates, FLUOROSULFATE, MOLECULAR-STRUCTURE, MONOXIDE, solid-state structures, superacidic systems, UNDECAFLUORODIANTIMONATE(V), VIBRATIONAL-SPECTRA, WEAKLY COORDINATING ANIONS, X-RAY-DIFFRACTION},
	isbn = {0947-6539},
	url = {<Go to ISI>://000182381600002},
	author = {Willner, H. and Aubke, F.}
}
@article {770,
	title = {sigma-bonded metal carbonyl cations and their derivatives: Syntheses and structural, spectroscopic, and bonding principles},
	journal = {Organometallics},
	volume = {22},
	number = {18},
	year = {2003},
	note = {ISI Document Delivery No.: 716AGTimes Cited: 22Cited Reference Count: 150},
	month = {Sep},
	pages = {3612-3633},
	type = {Review},
	abstract = {Homoleptic sigma-bonded metal carbonyl cations (sigma-carbonyls) and their derivatives have grown in recent years into a large subgroup of mononuclear metal carbonyl complexes. They are at present formed by 17 elements, including the post transition metal mercury. Most are generated in superacids: the Lewis superacid SbF5 and the conjugate Bronsted-Lewis superacid HF-SbF5. Thermally stable salts are formed with the superacid anions [Sb2F11](-) and [SbF6](-). Many of the cations are superelectrophilic, with metals in oxidation states of +2 or +3. Three different synthetic routes are developed: reductive (A) or solvolytic carbonylations (B) and oxidative methods (C). Considerable progress has been made by replacing the Lewis superacid SbF5 as reaction medium by the conjugate Bronsted-Lewis superacid HF-SbF5. This allows reactions to proceed faster in a homogeneous phase and to produce crystalline materials. In total 27 mostly recent molecular structures have been obtained, including that of [Ir(CO)(6)] [SbF6](3)(.)4HF, the first HF solvate with one of the HF molecules coordinated in an isotridentate mode to three carbon atoms of the cation. Due to the electrophilic nature of the carbonyl carbon in fluoroantimonate salts of metal carbonyl cations, extended structures are formed via significant interionic C{\textendash}- F contacts. A new a-bonded carbonyl, (CF3)(3)BCO, which has been fully characterized, expands the existence range of metal carbonyl cations to group 13. The large amount of spectroscopic and structural information accumulated is used to present a conceptually simple bonding model.},
	keywords = {CONCENTRATED SULFURIC-ACID, DENSITY-FUNCTIONAL CALCULATION, EFFECTIVE IONIC-RADII, HSO3F-SBF5, LEWIS SUPERACID, MAS-NMR-SPECTRA, MOLECULAR-STRUCTURE, NUCLEAR-MAGNETIC-RESONANCE, VIBRATIONAL-SPECTRA, WEAKLY COORDINATING ANIONS, X-RAY},
	isbn = {0276-7333},
	url = {<Go to ISI>://000185006200002},
	author = {Willner, H. and Aubke, F.}
}
@article {5221,
	title = {Superelectrophilic tetrakis(carbonyl)palladium(II)- and -platinum(II) undecafluorodiantimonate(V), [Pd(CO)(4)][Sb2F11](2) and [Pt(CO)(4)][Sb2F11](2): Syntheses, physical and spectroscopic properties, their crystal, molecular, and extended structures, and},
	journal = {Journal of the American Chemical Society},
	volume = {123},
	number = {4},
	year = {2001},
	note = {ISI Document Delivery No.: 396RTTimes Cited: 30Cited Reference Count: 181},
	month = {Jan},
	pages = {588-602},
	type = {Review},
	abstract = {{The salts [M(CO)(4)][Sb2F11](2)},
	keywords = {ADJUSTED ABINITIO, basis sets, GOLD(III) FLUOROSULFATE, HEXAKIS(CARBONYL)IRON(II), INFRARED-SPECTRA, MAS-NMR-SPECTRA, METAL-CARBONYL CATIONS, PSEUDOPOTENTIALS, TRANSITION-ELEMENTS, UNDECAFLUORODIANTIMONATE(V), VIBRATIONAL-SPECTRA, WEAKLY COORDINATING ANIONS},
	isbn = {0002-7863},
	url = {<Go to ISI>://000166650900009},
	author = {Willner, H. and Bodenbinder, M. and Brochler, R. and Hwang, G. and Rettig, S. J. and Trotter, J. and von Ahsen, B. and Westphal, U. and Jonas, V. and Thiel, W. and Aubke, F.}
}
@article {5221,
	title = {Superelectrophilic tetrakis(carbonyl)palladium(II)- and -platinum(II) undecafluorodiantimonate(V), [Pd(CO)(4)][Sb2F11](2) and [Pt(CO)(4)][Sb2F11](2): Syntheses, physical and spectroscopic properties, their crystal, molecular, and extended structures, and},
	journal = {Journal of the American Chemical Society},
	volume = {123},
	number = {4},
	year = {2001},
	note = {ISI Document Delivery No.: 396RTTimes Cited: 30Cited Reference Count: 181},
	month = {Jan},
	pages = {588-602},
	type = {Review},
	abstract = {{The salts [M(CO)(4)][Sb2F11](2)},
	keywords = {ADJUSTED ABINITIO, basis sets, GOLD(III) FLUOROSULFATE, HEXAKIS(CARBONYL)IRON(II), INFRARED-SPECTRA, MAS-NMR-SPECTRA, METAL-CARBONYL CATIONS, PSEUDOPOTENTIALS, TRANSITION-ELEMENTS, UNDECAFLUORODIANTIMONATE(V), VIBRATIONAL-SPECTRA, WEAKLY COORDINATING ANIONS},
	isbn = {0002-7863},
	url = {<Go to ISI>://000166650900009},
	author = {Willner, H. and Bodenbinder, M. and Brochler, R. and Hwang, G. and Rettig, S. J. and Trotter, J. and von Ahsen, B. and Westphal, U. and Jonas, V. and Thiel, W. and Aubke, F.}
}
@article {3866,
	title = {Superacid anions: Crystal and molecular structures of oxonium undecafluorodiantimonate(V), [H3O][Sb2F11], cesium fluorosulfate, CsSO3F, cesium hydrogen bis(fluorosulfate), Cs[H(SO3F)(2)], cesium tetrakis(fluorosulfato)aurate(III), Cs[Au(SO3F)(4)], cesium},
	journal = {Inorganic Chemistry},
	volume = {35},
	number = {21},
	year = {1996},
	note = {ISI Document Delivery No.: VL611Times Cited: 31Cited Reference Count: 90},
	month = {Oct},
	pages = {6113-6130},
	type = {Article},
	abstract = {{In order to understand the reasons for the low nucleophilicity of superacid anions, a systematic, comparative study of six superacid anions by single-crystal X-ray diffraction is undertaken. From magic acid, HSO3F-SbF5, surprisingly, single crystals of oxonium undecafluorodiantimonate(V), [H3O][Sb2F11], 1, are obtained. In the remaining five salts the cesium ion, Cs+, is used as the countercation. Both CsSO3F, 2, and its solvate Cs[H(SO3F)(2)], 3, are derived from the Bronsted superacid HSO3F. The conjugate noble metal superacid systems HSO3F-Au(SO3F)(3) and HSO3F-Pt(SO3F)(4) provide cesium tetrakis(fluorosulfato)aurate(III) Cs[Au(SO3F)(4)], 4, and cesium hexakis (fluorosulfato)platinate(IV) Cs-2[Pt(SO3F)(6)], 5. Cesium hexakis (fluorosulfato)antimonate(V) Cs[Sb(SO3F)(6)], 6, whose synthesis is described here in detail, provides evidence for the possible existence of a new conjugate superacid system, HSO3F-Sb(SO3F)(5). Crystals of [H3O][Sb2F11] (1, H3F11OSb2) are orthorhombic},
	keywords = {ACIDS, BEHAVIOR, CATIONS, CONSTANTS, DERIVATIVES, FLUORIDE, FLUOROSULFATE, GOLD(III), TRIS(FLUOROSULFATE), VIBRATIONAL-SPECTRA, WEAKLY COORDINATING ANIONS},
	isbn = {0020-1669},
	url = {<Go to ISI>://A1996VL61100024},
	author = {Zhang, D. L. and Rettig, S. J. and Trotter, J. and Aubke, F.}
}
@article {3866,
	title = {Superacid anions: Crystal and molecular structures of oxonium undecafluorodiantimonate(V), [H3O][Sb2F11], cesium fluorosulfate, CsSO3F, cesium hydrogen bis(fluorosulfate), Cs[H(SO3F)(2)], cesium tetrakis(fluorosulfato)aurate(III), Cs[Au(SO3F)(4)], cesium},
	journal = {Inorganic Chemistry},
	volume = {35},
	number = {21},
	year = {1996},
	note = {ISI Document Delivery No.: VL611Times Cited: 31Cited Reference Count: 90},
	month = {Oct},
	pages = {6113-6130},
	type = {Article},
	abstract = {{In order to understand the reasons for the low nucleophilicity of superacid anions, a systematic, comparative study of six superacid anions by single-crystal X-ray diffraction is undertaken. From magic acid, HSO3F-SbF5, surprisingly, single crystals of oxonium undecafluorodiantimonate(V), [H3O][Sb2F11], 1, are obtained. In the remaining five salts the cesium ion, Cs+, is used as the countercation. Both CsSO3F, 2, and its solvate Cs[H(SO3F)(2)], 3, are derived from the Bronsted superacid HSO3F. The conjugate noble metal superacid systems HSO3F-Au(SO3F)(3) and HSO3F-Pt(SO3F)(4) provide cesium tetrakis(fluorosulfato)aurate(III) Cs[Au(SO3F)(4)], 4, and cesium hexakis (fluorosulfato)platinate(IV) Cs-2[Pt(SO3F)(6)], 5. Cesium hexakis (fluorosulfato)antimonate(V) Cs[Sb(SO3F)(6)], 6, whose synthesis is described here in detail, provides evidence for the possible existence of a new conjugate superacid system, HSO3F-Sb(SO3F)(5). Crystals of [H3O][Sb2F11] (1, H3F11OSb2) are orthorhombic},
	keywords = {ACIDS, BEHAVIOR, CATIONS, CONSTANTS, DERIVATIVES, FLUORIDE, FLUOROSULFATE, GOLD(III), TRIS(FLUOROSULFATE), VIBRATIONAL-SPECTRA, WEAKLY COORDINATING ANIONS},
	isbn = {0020-1669},
	url = {<Go to ISI>://A1996VL61100024},
	author = {Zhang, D. L. and Rettig, S. J. and Trotter, J. and Aubke, F.}
}
