@article {1296,
	title = {Dynamic C-13 NMR studies of ligand exchange in linear (d(10)) silver(I) and gold(I) and square-planar (d(8)) rhodium(I) homoleptic metal carbonyl cations in superacidic media},
	journal = {Magnetic Resonance in Chemistry},
	volume = {43},
	number = {7},
	year = {2005},
	note = {ISI Document Delivery No.: 936FUTimes Cited: 0Cited Reference Count: 21},
	month = {Jul},
	pages = {520-527},
	type = {Article},
	abstract = {The dynamic CO exchange of the monovalent metal carbonyl cations [Ag((CO)-C-13)](+), [Au((CO)-C-13)(2)](+)-Au((CO)-C-13) SO3F and [Rh((CO)-C-12)(4-x)((CO)-C-13)(x)](+) (x <= 1) in superacidic solutions was studied by variable-temperature C-13 NMR methods. The exchange rates are strongly dependent on the acidity of the solvent, the concentration of metal carbonyl cations and temperature. Whereas a suitable exchange rate of the Ag(I) system is only accessible in magic acid (HSO3F-SbF5), the more stable Au(I) and Rh(I) systems were studied in the less acidic fluorosulfuric acid. Selected solutions of Ag(I), Rh(I) and Au(I) yielded activation barriers Delta G* of 42.7, 43.5, and 56.2 kJ mol(-1) respectively. Copyright (c) 2005 John Wiley \& Sons, Ltd.},
	keywords = {C-13 NMR, CO exchange, CRYSTAL, dynamic NMR, fluorosulfuric acid, GOLD, HINDERED INTERNAL ROTATION, HSO3F-SBF5, magic acid, metal carbonyl cations, NMR, NUCLEAR-MAGNETIC-RESONANCE, rhodium, silver, UNDECAFLUORODIANTIMONATE(V), VIBRATIONAL-SPECTRA},
	isbn = {0749-1581},
	url = {<Go to ISI>://000229841700003},
	author = {von Ahsen, B. and Bach, C. and Balzer, G. and Bley, B. and Bodenbinder, M. and Hagele, G. and Willner, H. 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 {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 {762,
	title = {Cationic carbonyl complexes of rhodium(I) and rhodium(III): Syntheses, vibrational spectra, NMR studies, and molecular structures of tetrakis(carbonyl)rhodium(I) heptachlorodialuminate and -gallate, [Rh(CO)(4)][Al2Cl7] and [Rh(CO)(4)][Ga2Cl7]},
	journal = {Inorganic Chemistry},
	volume = {42},
	number = {12},
	year = {2003},
	note = {ISI Document Delivery No.: 688AXTimes Cited: 6Cited Reference Count: 73},
	month = {Jun},
	pages = {3801-3814},
	type = {Article},
	abstract = {{Dimeric rhodium(I) bis(carbonyl) chloride, [Rh(CO)(2)(mu-Cl)](2), is found to be a useful and convenient starting material for the syntheses of new cationic carbonyl complexes of both rhodium(l) and rhodium(III). Its reaction with the Lewis acids AlCl3 or GaCl3 produces in a CO atmosphere at room temperature the salts [Rh(CO)(4)][M2CI7] (M = Al, Ga), which are characterized by Raman spectroscopy and single-crystal X-ray diffraction. Crystal data for [Rh(CO)(4)][Al2Cl7]: triclinic, space group P1 (No. 2); a = 9.705(3)},
	keywords = {ACIDS, ANIONS, CO, CRYSTAL, EXCHANGE, IR, metals, MONOXIDE, RH, UNDECAFLUORODIANTIMONATE(V)},
	isbn = {0020-1669},
	url = {<Go to ISI>://000183410900016},
	author = {von Ahsen, B. and Bach, C. and Berkei, M. and Kockerling, M. and Willner, H. and Hagele, G. and Aubke, F.}
}
@article {571,
	title = {[Co(Co)(5)][(CF3)(3)BF]: A stable salt of a homoleptic trigonal-bipyramidal metal-carbonyl cation},
	journal = {Angewandte Chemie-International Edition},
	volume = {42},
	number = {18},
	year = {2003},
	note = {ISI Document Delivery No.: 681QPTimes Cited: 11Cited Reference Count: 34},
	pages = {2077-2079},
	type = {Article},
	keywords = {ACIDS, ANIONS, borates, carbonyl ligands, CO, cobalt complexes, MOLECULAR-STRUCTURE, RH, structure elucidation, superacids, UNDECAFLUORODIANTIMONATE(V), VIBRATIONAL-SPECTRA, X-RAY-DIFFRACTION},
	isbn = {1433-7851},
	url = {<Go to ISI>://000183047100021},
	author = {Bernhardt, E. and Finze, M. and Willner, H. and Lehmann, C. W. 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 {502,
	title = {Experimental and calculated molecular structures and high symmetry conformations of [Sb2F11](-) (D-4h) and 1,4-C4H4N2 center dot 2SbF(5) (D-2h)},
	journal = {Solid State Sciences},
	volume = {4},
	number = {11-12},
	year = {2002},
	note = {ISI Document Delivery No.: 634TJTimes Cited: 8Cited Reference Count: 52},
	month = {Nov-Dec},
	pages = {1457-1463},
	type = {Article},
	abstract = {Antimony(V) fluoride, SbF5, forms a molecular adduct with pyrazine (1,4-diazine) of the composition 1,4-C4H4N2.2SbF5. Its molecular structure is obtained by single crystal X-ray diffraction. Crystal data of pyrazine.2SbF(5): orthorhombic, spacegroup Pbca ($\#$ 61); a = 8.8052(8) Angstrom; b = 9.948(1) Angstrom; c = 12.297(2) Angstrom; V = 1077.1(2) Angstrom(3); Z = 4; T = 173(1) K; R-1(I > 3sigma (I)) = 0.031; wR(2) = 0.083. The Sb-F-4(eq) planes are eclipsed and the planar C4H4N2 ring is at a 45degrees angle to give D-2h symmetry for pyrazine.2SbF(5). A very similar high symmetry conformation of pointgroup D-4h is found for the [Sb2F11](-) anion in the metal carbonyl salts [Rh(CO)(4)][Sb2F11], [Au(CO)(2)][Sb2F11] and in [H3F2][Sb2F11]. Structural data for pyrazine.2SbF(5) and [Sb2F11](-) from [H3F2][Sb2F11], as well as vibrational data for [Sb2F11](-) (D-4h) are compared to calculated (DFT-B3LYP) data. According to the DFT calculations, the conformation for the[Sb2F11](-) anion (D-4h) and pyrazine.2SbF(5) (D-2h) are both eclipsed with respect to the SbF5-groups and eclipsed with respect to the pyrazine plane in pyrazine.2SbF(5) in their respective ground states. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.},
	keywords = {ADDUCTS, antimony(V) fluoride, CATIONS, CRYSTAL, F-19, fluoroantimonate anion, HEXACARBONYLS, high symmetry conformation, Lewis acid-base adducts, N-donor complex of antimony(V) fluoride, superacid anion, UNDECAFLUORODIANTIMONATE(V), VIBRATIONAL-SPECTRA},
	isbn = {1293-2558},
	url = {<Go to ISI>://000180356800016},
	author = {Sham, I. H. T. and Patrick, B. O. and von Ahsen, B. and von Ahsen, S. and Willner, H. and Thompson, R. C. and Aubke, F.}
}
@article {502,
	title = {Experimental and calculated molecular structures and high symmetry conformations of [Sb2F11](-) (D-4h) and 1,4-C4H4N2 center dot 2SbF(5) (D-2h)},
	journal = {Solid State Sciences},
	volume = {4},
	number = {11-12},
	year = {2002},
	note = {ISI Document Delivery No.: 634TJTimes Cited: 8Cited Reference Count: 52},
	month = {Nov-Dec},
	pages = {1457-1463},
	type = {Article},
	abstract = {Antimony(V) fluoride, SbF5, forms a molecular adduct with pyrazine (1,4-diazine) of the composition 1,4-C4H4N2.2SbF5. Its molecular structure is obtained by single crystal X-ray diffraction. Crystal data of pyrazine.2SbF(5): orthorhombic, spacegroup Pbca ($\#$ 61); a = 8.8052(8) Angstrom; b = 9.948(1) Angstrom; c = 12.297(2) Angstrom; V = 1077.1(2) Angstrom(3); Z = 4; T = 173(1) K; R-1(I > 3sigma (I)) = 0.031; wR(2) = 0.083. The Sb-F-4(eq) planes are eclipsed and the planar C4H4N2 ring is at a 45degrees angle to give D-2h symmetry for pyrazine.2SbF(5). A very similar high symmetry conformation of pointgroup D-4h is found for the [Sb2F11](-) anion in the metal carbonyl salts [Rh(CO)(4)][Sb2F11], [Au(CO)(2)][Sb2F11] and in [H3F2][Sb2F11]. Structural data for pyrazine.2SbF(5) and [Sb2F11](-) from [H3F2][Sb2F11], as well as vibrational data for [Sb2F11](-) (D-4h) are compared to calculated (DFT-B3LYP) data. According to the DFT calculations, the conformation for the[Sb2F11](-) anion (D-4h) and pyrazine.2SbF(5) (D-2h) are both eclipsed with respect to the SbF5-groups and eclipsed with respect to the pyrazine plane in pyrazine.2SbF(5) in their respective ground states. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.},
	keywords = {ADDUCTS, antimony(V) fluoride, CATIONS, CRYSTAL, F-19, fluoroantimonate anion, HEXACARBONYLS, high symmetry conformation, Lewis acid-base adducts, N-donor complex of antimony(V) fluoride, superacid anion, UNDECAFLUORODIANTIMONATE(V), VIBRATIONAL-SPECTRA},
	isbn = {1293-2558},
	url = {<Go to ISI>://000180356800016},
	author = {Sham, I. H. T. and Patrick, B. O. and von Ahsen, B. and von Ahsen, S. and Willner, H. and Thompson, R. C. and Aubke, F.}
}
@article {536,
	title = {The synthesis, vibrational spectra, and molecular structure of [Ir(CO)(6)][SbF6](3)center dot 4HF - The first structurally characterized salt with a tripositive, homoleptic metal carbonyl cation and the first example of a tetrahedral hydrogen-bonded (HF)(},
	journal = {Journal of the American Chemical Society},
	volume = {124},
	number = {28},
	year = {2002},
	note = {ISI Document Delivery No.: 573QWTimes Cited: 14Cited Reference Count: 58},
	month = {Jul},
	pages = {8371-8379},
	type = {Article},
	abstract = {{The reductive carbonylation of IrF6 in a dilute solution of SbF5 in anhydrous HF (1:6 by volume) produces surprisingly at 25 degreesC and 1.5 atm CO the complex salt [Ir(CO)(6)][SbF6](3).4HF, while [Ir(CO)(6)][Sb2F11](3) is obtained in liquid SbF5 under similar conditions. Vibrational spectra in the CO stretching range for both salts and [Ir(CO)(6)](3+)((solv)) are identical within error limits, and v(CO)(av) is with 2269 cm(-1) the highest average stretching frequency so far observed for octahedral metal carbonyl cations. A vibrational assignment supported by DFT calculations is presented, and the vibrational fundamentals are compared to those of [OS(CO)(6)](2+). The molecular structure of [Ir(CO)(6)][SbF6](3).4HF is determined by single-crystal X-ray diffraction. Crystal data for [Ir(CO)(6)][SbF6](3).4HF: rhombohedral, R3c (No. 161)},
	keywords = {<IR(CO)(6)>(3+), CARBOCATIONS, CHEMISTRY, CRYSTAL-STRUCTURES, IR, MO, OS, RU, SUPERACID MEDIA, UNDECAFLUORODIANTIMONATE(V)},
	isbn = {0002-7863},
	url = {<Go to ISI>://000176843200032},
	author = {von Ahsen, B. and Berkei, M. and Henkel, G. and Willner, H. and Aubke, F.}
}
@article {374,
	title = {Tris(trifluoromethyl)borane carbonyl, (CF3)(3)BCO - Synthesis, physical, chemical and spectroscopic properties, gas phase, and solid state structure},
	journal = {Journal of the American Chemical Society},
	volume = {124},
	number = {51},
	year = {2002},
	note = {ISI Document Delivery No.: 628QATimes Cited: 49Cited Reference Count: 86},
	month = {Dec},
	pages = {15385-15398},
	type = {Article},
	abstract = {Tris(trifluoromethyl)borane carbonyl, (CF3)(3)BCO, is obtained in high yield by the solvolysis of K[B(CF3)(4)] in concentrated sulfuric acid. The in situ hydrolysis of a single bonded CF3 group is found to be a simple, unprecedented route to a new borane carbonyl. The related, thermally unstable borane carbonyl, (C6F5)(3)BCO, is synthesized for comparison purposes by the isolation of (C6F5)(3)B in a matrix of solid CO at 16 K and subsequent evaporation of excess CO at 40 K. The colorless liquid and vapor of (CF3)3BCO decomposes slowly at room temperature. In the gas phase t(1/2) is found to be 45 min. In the presence of a large excess of (CO)-C-13, the carbonyl substituent at boron undergoes exchange, which follows a first-order rate law. Its temperature dependence yields an activation energy (EA) of 112 kJ mol(-1). Low-pressure flash thermolysis of (CF3)3BCO with subsequent isolation of the products in low-temperature matrixes, indicates a lower thermal stability of the (CF3)3B fragment, than is found for (CF3)3BCO. Toward nucleophiles (CF3)3BCO reacts in two different ways: Depending on the nucleophilicity of the reagent and the stability of the adducts formed, nucleophilic substitution of CO or nucleophilic addition to the C atom of the carbonyl group are observed. A number of examples for both reaction types are presented in an overview. The molecular structure of (CF3)(3)BCO in the gas phase is obtained by a combined microwave-electron diffraction analysis and in the solid state by single-crystal X-ray diffraction. The molecule possesses C3 symmetry, since the three CF3 groups are rotated off the two possible positions required for C3, symmetry. All bond parameters, determined in the gas phase or in the solid state, are within their standard deviations in fair agreement, except for internuclear distances most noticeably the B-CO bond lengths, which is 1.69(2) Angstrom in the solid state and 1.617(12) Angstrom in the gas phase. A corresponding shift of nu(CO) from 2267 cm(-1) in the solid state to 2251 cm-1 in the gas phase is noted in the vibrational spectra. The structural and vibrational study is supported by DFT calculations, which provide, in addition to the equilibrium structure, confirmation of experimental vibrational wavenumbers, IR-band intensities, atomic charge distribution, the dipole moment, the B-CO bond energy, and energies for the elimination of CF2 from (CF3)(x)BF3-x1 = 1-3. In the vibrational analysis 21 of the expected 26 fundamentals are observed experimentally. The B-11-, C-13-, and F-19-NMR data, as well as the structural parameters of (CF3)(3)BCO, are compared with those of related compounds.},
	keywords = {= F, COMPLEXES, CRYSTAL, DERIVATIVES, IR, MICROWAVE-SPECTRUM, MOLECULAR-STRUCTURES, NMR, UNDECAFLUORODIANTIMONATE(V), X-RAY-DIFFRACTION},
	isbn = {0002-7863},
	url = {<Go to ISI>://000180006600046},
	author = {Finze, M. and Bernhardt, E. and Terheiden, A. and Berkei, M. and Willner, H. and Christen, D. and Oberhammer, 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 {4962,
	title = {Bis(carbonyl)platinum(II) derivatives: Molecular structure of cis-Pt(CO)(2)(SO3F)(2), complete vibrational analysis of cis-Pt(CO)(2)Cl-2, and attempted synthesis of cis-Pt(CO)(2)F-2},
	journal = {Inorganic Chemistry},
	volume = {39},
	number = {20},
	year = {2000},
	note = {ISI Document Delivery No.: 361DNTimes Cited: 12Cited Reference Count: 91},
	month = {Oct},
	pages = {4424-4432},
	type = {Article},
	abstract = {{As part of a comprehensive study of square planar palladium(II) and platinum(II) carbonyl derivatives, the molecular structure of cis-Pt(CO)(2)(SO3F)(2), the complete vibrational spectra of cis-Pt(CO)(2)Cl-2 and the attempted synthesis of cis-Pt(CO)(2)F-2 an reported. cis-Pt(CO)(2)(SO3F)(2) is isostructural with cis-Pd(CO) (2)(SO3F)(2) and crystallizes in the monoclinic space group P2(1)/n (no. 14). Crystal data: a = 7.419(1) Angstrom; b = 14.751(2) Angstrom; c 8.634(1) Angstrom; beta = 89.95(1)degrees; V = 934.9(2) Angstrom(3); Z = 4; T = 300 K; R [F-o > 4 sigma(F-o)] = 0.0447 and wR2 = 0.1097. The internal bond parameters of the cis-Pt(CO)(2)(SO3F)(2) are compared to those of cis-Pd(CO)(2)(SO3F)(2), cis-Pt(CO)(2)Cl-2, and [M(CO)(4)](2+)},
	keywords = {CARBONYL-COMPLEXES, CRYSTAL-STRUCTURE, FLUOROSULFATE, HALIDE LIGANDS, INORGANIC, LATE TRANSITION-ELEMENTS, NOBLE-METALS, OLIGOMERS, platinum, SPECTRA, UNDECAFLUORODIANTIMONATE(V)},
	isbn = {0020-1669},
	url = {<Go to ISI>://000089707500008},
	author = {von Ahsen, B. and Wartchow, R. and Willner, H. and Jonas, V. and Aubke, F.}
}
@article {4961,
	title = {{The reactions of the third transition series metal hexafluorides, MF6},
	journal = {Journal of Fluorine Chemistry},
	volume = {102},
	number = {1-2},
	year = {2000},
	note = {ISI Document Delivery No.: 302YMTimes Cited: 8Cited Reference Count: 77},
	month = {Mar},
	pages = {243-252},
	type = {Article},
	abstract = {{The reactions of the third transition (5d) series metal hexafluorides PtF6, IrF6, OsF6, ReF6 and WF6 with CO are studied in the Lewis superacid SbF5, the Bronsted superacid HF and the conjugate Bronsted-Lewis superacid HF-SbF5, in order to evaluate their potential as reactants in reductive carbonylations. These reactions are aimed at the generation of homoleptic metal carbonyl cations of the type [M(CO)(n)](m+)},
	keywords = {<IR(CO)(6)>(3+), carbonyl fluoride, CO, FLUOROSULFATES, HEXACARBONYLS, homoleptic carbonyl complexes, INCLUDING STEREOISOMERS, metal hexafluorides, MOLECULAR-STRUCTURE, NOBLE-METALS, PALLADIUM(II), platinum, superacid, UNDECAFLUORODIANTIMONATE(V), VIBRATIONAL-SPECTRA},
	isbn = {0022-1139},
	url = {<Go to ISI>://000086394100033},
	author = {von Ahsen, B. and Bach, C. and Pernice, H. and Willner, H. 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 {4491,
	title = {Synthesis and structure of [{Mo(CO)(4)}(2)(cis-mu-F2SbF4)(3)](x)[Sb2F11](x): An ionic coordination polymer},
	journal = {Inorganic Chemistry},
	volume = {38},
	number = {16},
	year = {1999},
	note = {ISI Document Delivery No.: 226JVTimes Cited: 16Cited Reference Count: 35},
	month = {Aug},
	pages = {3684-3687},
	type = {Article},
	abstract = {{The oxidation of molybdenum hexacarbonyl, Mo(CO)(6), by antimony(V) fluoride, SbF5, at 60 degrees C in an excess of liquid SbF5, produces polymeric [{Mo(CO)(4)}(2)(cis-mu-F2SbF4)(3)](x)[Sb2F11](x) as the main product. Recrystallization from HF-SbF5 produces orange prismatic crystals, suitable for a single-crystal X-ray diffraction study. Crystals of [{Mo(CO)(4)}(2)(cis-mu-F2SbF4)(3)](x)[Sb2F11](x) are monoclinic, space group P2(1)/c (No. 14)},
	keywords = {ANIONS, COMPLEXES, CRYSTAL, FLUORIDE, FLUOROSULFATE, MOLYBDENUM, UNDECAFLUORODIANTIMONATE(V)},
	isbn = {0020-1669},
	url = {<Go to ISI>://000082017600016},
	author = {Brochler, R. and Freidank, D. and Bodenbinder, M. and Sham, I. H. T. and Willner, H. and Rettig, S. J. and Trotter, J. and Aubke, F.}
}
@article {4491,
	title = {Synthesis and structure of [{Mo(CO)(4)}(2)(cis-mu-F2SbF4)(3)](x)[Sb2F11](x): An ionic coordination polymer},
	journal = {Inorganic Chemistry},
	volume = {38},
	number = {16},
	year = {1999},
	note = {ISI Document Delivery No.: 226JVTimes Cited: 16Cited Reference Count: 35},
	month = {Aug},
	pages = {3684-3687},
	type = {Article},
	abstract = {{The oxidation of molybdenum hexacarbonyl, Mo(CO)(6), by antimony(V) fluoride, SbF5, at 60 degrees C in an excess of liquid SbF5, produces polymeric [{Mo(CO)(4)}(2)(cis-mu-F2SbF4)(3)](x)[Sb2F11](x) as the main product. Recrystallization from HF-SbF5 produces orange prismatic crystals, suitable for a single-crystal X-ray diffraction study. Crystals of [{Mo(CO)(4)}(2)(cis-mu-F2SbF4)(3)](x)[Sb2F11](x) are monoclinic, space group P2(1)/c (No. 14)},
	keywords = {ANIONS, COMPLEXES, CRYSTAL, FLUORIDE, FLUOROSULFATE, MOLYBDENUM, UNDECAFLUORODIANTIMONATE(V)},
	isbn = {0020-1669},
	url = {<Go to ISI>://000082017600016},
	author = {Brochler, R. and Freidank, D. and Bodenbinder, M. and Sham, I. H. T. and Willner, H. and Rettig, S. J. and Trotter, J. and Aubke, F.}
}
@article {3597,
	title = {Cationic iridium(III) carbonyl complexes: [Ir(CO)(6)](3+) and [Ir(CO)(5)Cl](2+)},
	journal = {Angewandte Chemie-International Edition in English},
	volume = {35},
	number = {17},
	year = {1996},
	note = {ISI Document Delivery No.: VM029Times Cited: 55Cited Reference Count: 27},
	month = {Sep},
	pages = {1974-1976},
	type = {Article},
	keywords = {carbonyl complexes, ELUCIDATION, FLUOROSULFATE, IR spectroscopy, iridium compounds, MOLECULAR-STRUCTURE, MONOXIDE, SPECTRA, STRUCTURE, UNDECAFLUORODIANTIMONATE(V)},
	isbn = {0570-0833},
	url = {<Go to ISI>://A1996VM02900023},
	author = {Bach, C. and Willner, H. and Wang, C. Q. and Rettig, S. J. and Trotter, J. and Aubke, F.}
}
@article {3597,
	title = {Cationic iridium(III) carbonyl complexes: [Ir(CO)(6)](3+) and [Ir(CO)(5)Cl](2+)},
	journal = {Angewandte Chemie-International Edition in English},
	volume = {35},
	number = {17},
	year = {1996},
	note = {ISI Document Delivery No.: VM029Times Cited: 55Cited Reference Count: 27},
	month = {Sep},
	pages = {1974-1976},
	type = {Article},
	keywords = {carbonyl complexes, ELUCIDATION, FLUOROSULFATE, IR spectroscopy, iridium compounds, MOLECULAR-STRUCTURE, MONOXIDE, SPECTRA, STRUCTURE, UNDECAFLUORODIANTIMONATE(V)},
	isbn = {0570-0833},
	url = {<Go to ISI>://A1996VM02900023},
	author = {Bach, C. and Willner, H. and Wang, C. Q. and Rettig, S. J. and Trotter, J. and Aubke, F.}
}
@article {3844,
	title = {Homoleptic carbonyl cations of palladium(I), palladium(II), platinum(II), and gold(I) - Simplified synthetic routes to their fluoroantimonate(V) salts},
	journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie},
	volume = {74},
	number = {11},
	year = {1996},
	note = {ISI Document Delivery No.: WC124Times Cited: 8Cited Reference Count: 68},
	month = {Nov},
	pages = {1952-1958},
	type = {Article},
	abstract = {{The original synthetic routes to the new noble metal carbonyl cations [Au(CO)(2)](+) and [M(CO)(4)](2+)},
	keywords = {ACIDS, and Pt(II), carbonylations in strong acidic media, COMPLEXES, DERIVATIVES, FLUOROSULFATES, MAS NMR-SPECTRA, metal carbonyl cations of Au(I), MONOXIDE, NOBLE-METALS, Pd(I), Pd(II), reactions in liquid SbF5, reductive carbonylation in liquid SbF5, solvolysis, UNDECAFLUORODIANTIMONATE(V), VIBRATIONAL-SPECTRA},
	isbn = {0008-4042},
	url = {<Go to ISI>://A1996WC12400009},
	author = {Wang, C. Q. and Siu, S. C. and Hwang, G. and Bach, C. and Bley, B. and Bodenbinder, M. and Willner, H. and Aubke, F.}
}
@article {3842,
	title = {Solvolysis reactions in liquid antimony (V) fluoride. A convenient and versatile synthetic method},
	journal = {European Journal of Solid State and Inorganic Chemistry},
	volume = {33},
	number = {9},
	year = {1996},
	note = {ISI Document Delivery No.: VK527Times Cited: 9Cited Reference Count: 71},
	pages = {917-930},
	type = {Article},
	abstract = {{Solvolysis reactions of various fluorosulfates in liquid antimony (V) fluoride allow the synthesis of a wide range of fluoroantimonate (V) salts with main group, organometallic and transition metal cations. In the presence of carbon monoxide, CO, at pressures of 0.5 to 2.0 atmospheres a new group of homoleptic carbonyl cations of electronrich metals (Hg, Au, Pt, Pd, Ir, Ru, and Os) form with [Sb2F11](-) as anion. The salts show relatively high thermal stability (> 100 degrees C). The geometries of the cations [Au(CO)(2)](+), [Hg(CO)(2)](2+) (linear) and [M(CO)(4)](2+)},
	keywords = {CATIONS, CRYSTAL, FLUOROSULFATES, MAGNETIC-PROPERTIES, MAS NMR-SPECTRA, MOLECULAR-STRUCTURE, NOBLE-METALS, TRIS(FLUOROSULFATE), UNDECAFLUORODIANTIMONATE(V), VIBRATIONAL-SPECTRA},
	isbn = {0992-4361},
	url = {<Go to ISI>://A1996VK52700012},
	author = {Wang, C. and Hwang, G. and Siu, S. C. and Aubke, F. and Bley, B. and Bodenbinder, M. and Bach, C. and Willner, H.}
}
@article {3843,
	title = {Synthesis, molecular structure, and vibrational spectra of mer-tris(carbonyl)iridium(III)fluorosulfate, mer-Ir(CO)(3)(SO3F)(3)},
	journal = {Inorganic Chemistry},
	volume = {35},
	number = {5},
	year = {1996},
	note = {ISI Document Delivery No.: TY260Times Cited: 21Cited Reference Count: 36},
	month = {Feb},
	pages = {1279-1285},
	type = {Article},
	abstract = {{Addition of carbon monoxide (0.5-2 atm) to iridium(III) fluorosulfate, Ir(SO3F)(3), dissolved in HSO3F over 4 days and at 60 degrees C, results in the quantitative formation of tris(carbonyl)iridium(III) fluorosulfate Ir(CO)(3)(SO3F)(3) Slow evaporation of the solvent produces single crystals of mer-Ir(CO)(3)(SO3F)(3). Crystal structure data for mer-Ir(CO)(3)(SO3F)(3): monoclinic, space group P2(1)/c},
	keywords = {DERIVATIVES, FLUOROSULFATES, GOLD, palladium, SYSTEM, UNDECAFLUORODIANTIMONATE(V)},
	isbn = {0020-1669},
	url = {<Go to ISI>://A1996TY26000029},
	author = {Wang, C. Q. and Lewis, A. R. and Batchelor, R. J. and Einstein, F. W. B. and Willner, H. and Aubke, F.}
}
@article {3228,
	title = {CADY,GEORGE CONTRIBUTION TO NOBLE-METAL CHEMISTRY},
	journal = {Journal of Fluorine Chemistry},
	volume = {71},
	number = {2},
	year = {1995},
	note = {ISI Document Delivery No.: QV343Times Cited: 2Cited Reference Count: 18George H Cady Symposium on Inorganic Chemistry, at the 207th Meeting of the American-Chemical-SocietyMAR 14-17, 1994SAN DIEGO, CAAMER CHEM SOC},
	month = {Apr},
	pages = {199-200},
	type = {Proceedings Paper},
	keywords = {ESR SPECTROSCOPY, FLUOROSULFATE DERIVATIVES, GOLD, MAGNETIC PROPERTIES, MOLECULAR-STRUCTURE, NOBLE-METAL CHEMISTRY, PALLADIUM(II), SILVER DIFLUORIDE, SILVER(II), SUPERACID SYSTEMS, SYNTHESES, UNDECAFLUORODIANTIMONATE(V)},
	isbn = {0022-1139},
	url = {<Go to ISI>://A1995QV34300024},
	author = {Aubke, F.}
}
@article {3227,
	title = {THE GENERATION OF UNUSUAL NOBLE-METAL CATIONS IN FLUORO ACIDS AND SUPER ACIDS, AND THEIR SPECTROSCOPIC PROPERTIES},
	journal = {Journal of Fluorine Chemistry},
	volume = {72},
	number = {2},
	year = {1995},
	note = {ISI Document Delivery No.: RD582Times Cited: 13Cited Reference Count: 39International Conference on Fluorine Chemistry 94 KyotoJUL 27-30, 1994KYOTO, JAPANJapan Soc Promot Sci, 155th Comm Fluorine Chem, Chem Soc Japan, Electrochem Soc Japan, Pharm Soc Japan, Soc Synth Organ Chem},
	month = {Jun},
	pages = {195-201},
	type = {Proceedings Paper},
	abstract = {{Two types of highly electrophilic cations, {\textquoteright}bare{\textquoteright} M(2+) or carbonyl cations, formed by the noble metals palladium and platinum (Group 10) and silver and gold (Group 11) in low oxidation states (+1 or +2) are generated in highly acidic media. The acidic media consists of: the Bronsted superacid HSO3F; the Lewis superacid SbF5; and the conjugate superacid HSO3F-SbF5. Derived from these superacids are the very weakly nucleophilic anions SO3F- or Sb2F11- as counterions to stabilize the cations in solids. Finally, stabilization of the highly electrophilic cations by coordination to CO leads to isolable complexes, unprecedented in transition-metal chemistry in their structural, spectroscopic and bonding characteristics. The cations discussed include, in addition to {\textquoteright}bare{\textquoteright} M(2+) (M=Ag or Au): linear [M(CO)(n)](+)},
	keywords = {CARBONYL, FLUORO ACIDS, FLUOROSULFATE DERIVATIVES, GOLD, IONS, IR spectroscopy, MOLECULAR-STRUCTURE, NMR, NOBLE-METAL CATIONS, PALLADIUM(II), SILVER(II), SPECTROSCOPY, SUPER ACIDS, UNDECAFLUORODIANTIMONATE(V), X-RAY CRYSTAL STRUCTURES},
	isbn = {0022-1139},
	url = {<Go to ISI>://A1995RD58200007},
	author = {Aubke, F.}
}
@article {3255,
	title = {THE USE OF FLUOROSULFURIC ACID, MAGIC ACID AND LIQUID ANTIMONY(V) FLUORIDE AS MEDIA TO GENERATE, STABILIZE AND STUDY METAL-CARBONYL CATIONS},
	journal = {Journal of Fluorine Chemistry},
	volume = {71},
	number = {2},
	year = {1995},
	note = {ISI Document Delivery No.: QV343Times Cited: 0Cited Reference Count: 11George H Cady Symposium on Inorganic Chemistry, at the 207th Meeting of the American-Chemical-SocietyMAR 14-17, 1994SAN DIEGO, CAAMER CHEM SOC},
	month = {Apr},
	pages = {201-202},
	type = {Proceedings Paper},
	keywords = {antimony(V) fluoride, CATIONS, fluorosulfuric acid, IR spectroscopy, magic acid, METAL CARBONYL, NMR spectroscopy, SYNTHESIS, UNDECAFLUORODIANTIMONATE(V)},
	isbn = {0022-1139},
	url = {<Go to ISI>://A1995QV34300025},
	author = {Bodenbinder, M. and Willner, H. and Aubke, F.}
}
