@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 {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 {4977,
	title = {Syntheses, molecular structures, and vibrational spectra of chloropentacarbonylrhodium(III) and -iridium(III) undecafluorodiantimonate(V), [Rh(CO)(5)Cl][Sb2F11](2) and [Ir(CO)(5)Cl][Sb2F11](2): An experimental and density functional study},
	journal = {Inorganic Chemistry},
	volume = {39},
	number = {9},
	year = {2000},
	note = {ISI Document Delivery No.: 311CJTimes Cited: 10Cited Reference Count: 91},
	month = {May},
	pages = {1933-1942},
	type = {Article},
	abstract = {{The reactions of either bis(mu-chloro)tetracarbonyldirhodium(I), [Rh(CO)(2()mu-Cl)](2), or chlorotricarbonyliridium(I), [Ir(CO)(3)Cl](n), in the conjugate Bronsted-Lewis superacid HF-SbF5 and in a CO atmosphere, produce [Rh-(CO)(5)Cl][Sb2F11](2) or [Ir(CO)(5)Cl][Sb2F11](2), respectively. In these oxidative carbonylation reactions, antimony(V) fluoride functions as an oxidizing agent. The reduced product is identified as 6SbF(3). 5SbF(5). [Rh(CO)(5)Cl][Sb2F11]2 is obtained in the form of single crystals. Crystal data: monoclinic, space group P2(1) (No. 4); a = 9.721(1)},
	keywords = {ATOMS, basis sets, BEHAVIOR, CARBONYL-COMPLEXES, CRYSTAL, ELEMENTS, ENERGY, FLUOROSULFATE, MAS-NMR-SPECTRA, ORBITAL METHODS, ROW},
	isbn = {0020-1669},
	url = {<Go to ISI>://000086867000015},
	author = {Willner, H. and Bach, C. and Wartchow, R. and Wang, C. Q. and Rettig, S. J. and Trotter, J. and Jonas, V. and Thiel, W. and Aubke, F.}
}
@article {4977,
	title = {Syntheses, molecular structures, and vibrational spectra of chloropentacarbonylrhodium(III) and -iridium(III) undecafluorodiantimonate(V), [Rh(CO)(5)Cl][Sb2F11](2) and [Ir(CO)(5)Cl][Sb2F11](2): An experimental and density functional study},
	journal = {Inorganic Chemistry},
	volume = {39},
	number = {9},
	year = {2000},
	note = {ISI Document Delivery No.: 311CJTimes Cited: 10Cited Reference Count: 91},
	month = {May},
	pages = {1933-1942},
	type = {Article},
	abstract = {{The reactions of either bis(mu-chloro)tetracarbonyldirhodium(I), [Rh(CO)(2()mu-Cl)](2), or chlorotricarbonyliridium(I), [Ir(CO)(3)Cl](n), in the conjugate Bronsted-Lewis superacid HF-SbF5 and in a CO atmosphere, produce [Rh-(CO)(5)Cl][Sb2F11](2) or [Ir(CO)(5)Cl][Sb2F11](2), respectively. In these oxidative carbonylation reactions, antimony(V) fluoride functions as an oxidizing agent. The reduced product is identified as 6SbF(3). 5SbF(5). [Rh(CO)(5)Cl][Sb2F11]2 is obtained in the form of single crystals. Crystal data: monoclinic, space group P2(1) (No. 4); a = 9.721(1)},
	keywords = {ATOMS, basis sets, BEHAVIOR, CARBONYL-COMPLEXES, CRYSTAL, ELEMENTS, ENERGY, FLUOROSULFATE, MAS-NMR-SPECTRA, ORBITAL METHODS, ROW},
	isbn = {0020-1669},
	url = {<Go to ISI>://000086867000015},
	author = {Willner, H. and Bach, C. and Wartchow, R. and Wang, C. Q. and Rettig, S. J. and Trotter, J. and Jonas, V. and Thiel, W. and Aubke, F.}
}
@article {4730,
	title = {The tetrakis(carbonyl)dioxoosmium(VI) cation: trans-[OsO2(CO)(4)](2+)},
	journal = {Angewandte Chemie-International Edition},
	volume = {39},
	number = {1},
	year = {2000},
	note = {ISI Document Delivery No.: 273GWTimes Cited: 5Cited Reference Count: 34},
	pages = {168-+},
	type = {Article},
	keywords = {C-13, carbonyl complexes, CATIONS, COMPLEXES, CRYSTAL-STRUCTURE, density functional calculations, MAS-NMR-SPECTRA, MOLECULAR-STRUCTURE, superacidic systems, UNDECAFLUORODIANTIMONATE(V), vibrational spectroscopy},
	isbn = {1433-7851},
	url = {<Go to ISI>://000084700400017},
	author = {Bernhardt, E. and Willner, H. and Jonas, V. and Thiel, W. and Aubke, F.}
}
@article {4473,
	title = {Hexakis(carbonyl)iron(II) undecafluorodiantimonate(V), [Fe(CO)(6)][Sb2F11](2), and -hexafluoroantimonate(V), [Fe(CO)(6)][SbF6](2), their syntheses, and spectroscopic and structural characterization by single crystal X-ray diffraction and normal coordinate},
	journal = {Journal of the American Chemical Society},
	volume = {121},
	number = {31},
	year = {1999},
	note = {ISI Document Delivery No.: 227UKTimes Cited: 32Cited Reference Count: 109},
	month = {Aug},
	pages = {7188-7200},
	type = {Review},
	abstract = {Hexakis/carbonyl iron(LI) undecafluorodiantimonate(V), [Fe(CO)(6)][Sb2F11](2) is conveniently prepared by the oxidative carbonylation of Fe(CO)(5) with XeF2 as external oxidizer in the conjugate Br phi nsted-Lewis superacid HF-SbF5. The colorless compound crystallizes from the reaction medium in high purity. The molecular structure is obtained by single-crystal X-ray diffraction. The cation is a regular octahedron, while the vertex-shared di-octahedral [Sb2F11](-) anion is distorted from D-4h symmetry by bending and rotational processes, due to significant interionic interactions, primarily of the FC type. Washing of [Fe(CO)(6)][Sb2F11](2) with anhydrous HF results in an unusual elution of SbF5 and the quantitative conversion to hexakis(carbonyl)iron(II) hexafluoroantimonate;(V) [Fe(CO)(6)][SbF6](2) The molecular structure of the salt shows octahedral ions with slight tetragonal distortions for the cation (elongation) and the anion (comprsssion). Both salts are thermally stable up to 150 degrees C, The averaged bond distances and the vibrational wavenumbers of [Fe(CO)(6)](2+) are nearly identical in both compounds. The [Fe(CO)(6)](2+) cation, the first and so far only isolated and structurally characterized dipositive, superelectrophilic carbonyl cation formed by a 3d-metal, is further characterized by a normal coordinate analysis (NCA). The obtained force constants are compared to those of the isoelectronic molecule Cr(CO)6. Changes in pi-back-bonding affect the F-CO/CO and F-CO/MC interaction force constants more strongly than the stretching force constants F-CO and F-MC All 13 fundamentals of [Fe(CO)(6)](2+) are detected and assigned with the help of the data obtained from the normal coordinate analysis and density functional calculations published previously. The electronic ground state (1)A(1g), of the [Fe(CO)(6)](2+) cation is established by magnetic susceptibility measurements of polycrystalline [Fe(CO)(6)][SbF6](2) and [Fe(CO)(6)][Sb2F11](2) between and 300 K. The magnetic impurity formed during synthesis is identified as Fe[SbF6](2) which has iron(II) in high spin (T-5(2g)) ground state. Consistent with a diamagnetic ground state are the single line in the Fe-57 Mossbauer spectrum (i.s. = -0.003(8) mm s(-1) relative to alpha-Fe), obtained on polycrystalline samples and the single sharp line in the C-13 NMR spectrum in DF solution at 178 ppm with J (Fe-57-C-13) of 19.2 Hz.},
	keywords = {C-13, COMPLEXES, CONSTANTS, IRON PENTACARBONYL, MAS-NMR-SPECTRA, METAL-CARBONYL CATIONS, MO, MOLECULAR-STRUCTURE, MONOXIDE, VIBRATIONAL-SPECTRA},
	isbn = {0002-7863},
	url = {<Go to ISI>://000082098200003},
	author = {Bernhardt, E. and Bley, B. and Wartchow, R. and Willner, H. and Bill, E. and Kuhn, P. and Sham, I. H. T. and Bodenbinder, M. and Brochler, R. and Aubke, F.}
}
@article {4159,
	title = {Homoleptic metal carbonyl cations of the electron-rich metals: Their generation in superacid media together with their spectroscopic and structural characterization},
	journal = {Angewandte Chemie-International Edition in English},
	volume = {36},
	number = {22},
	year = {1997},
	note = {ISI Document Delivery No.: YK253Times Cited: 18Cited Reference Count: 279},
	month = {Dec},
	pages = {2403-2425},
	type = {Review},
	keywords = {ANIONS, carbonyl complexes, CATIONS, CESIUM, FLUOROSULFATE, FLUOROSULFATE DERIVATIVES, GOLD(III), HEXAKIS(FLUOROSULFATO)ANTIMONATE(V), HIGHLY REDUCED ORGANOMETALLICS, MAS-NMR-SPECTRA, MOLECULAR-STRUCTURE, superacidic systems, synthetic methods, transition metals, TRANSITION-ELEMENTS, TRIFLUOROMETHYLATED, TRIS(PYRAZOLYL)BORATE, VIBRATIONAL-SPECTRA, WEAKLY COORDINATING},
	isbn = {0570-0833},
	url = {<Go to ISI>://A1997YK25300001},
	author = {Willner, H. and Aubke, F.}
}
