@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 = {://000183410900016}, author = {von Ahsen, B. and Bach, C. and Berkei, M. and Kockerling, M. and Willner, H. and Hagele, G. 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 = {(3+), CARBOCATIONS, CHEMISTRY, CRYSTAL-STRUCTURES, IR, MO, OS, RU, SUPERACID MEDIA, UNDECAFLUORODIANTIMONATE(V)}, isbn = {0002-7863}, url = {://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 = {://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 {3029, title = {MICROMORPHOLOGICAL AND C-13 NMR CHARACTERIZATION OF A HUMIC, LIGNIC, AND HISTIC FOLISOL FROM BRITISH-COLUMBIA}, journal = {Canadian Journal of Soil Science}, volume = {74}, number = {1}, year = {1994}, note = {ISI Document Delivery No.: NG042Times Cited: 9Cited Reference Count: 39}, month = {Feb}, pages = {1-15}, type = {Article}, abstract = {The thick folic (mainly upland forest) materials (> 40 cm of accumulated organic material) that occur in the Coastal Western Hemlock Biogeoclimatic Zone in British Columbia have not been described with regard to the spatial interrelationships of the soil constituents in context with the chemical composition of the different horizons. Micromorphological assessment and solid-state C-13 NMR were used to characterize the accumulated folic materials from a Lignic Folisol (northern Vancouver Island), Histic Folisol (Prince Rupert, BC) and a Humic Folisol (Queen Charlotte Islands, BC). Micromorphology provided information on the spatial relationships of the soil constituents and C-13 NMR provided data on the chemical components of the folic materials. Soil faunal activity, primarily from mites, was the dominant soil-forming process observed in the organic horizons of the Folisols, being especially prominent in the Lignic Folisol with the breakdown of woody materials. Solid state C-13 CPMAS NMR spectra facilitated distinguishing three main types of horizons: (1) Horizons derived from accumulated residues (L, Fr, and Hr) showing higher carbohydrate-like C and O-alkyl C values and lower total aromatics; (2) Horizons with advanced decomposition (Hr2, Oh1, and Hd) which were higher in alkyl C; and (3) Horizons derived from ligneous material (Fw and Hdw) where carbohydrate-like C was less than total aromatic C. Implications for adequate nutrient content and forest growth were inferred from the observed micromorphology and chemical composition of the folic materials.}, keywords = {C-13 NMR, CHEMICAL-COMPOSITION, DECOMPOSITION, FAUNAL ACTIVITY, FOLISOL, FOREST SOILS, IONIZATION MASS-SPECTROMETRY, IR, LITTER, MICROMORPHOLOGY, NITROGEN, NUCLEAR-MAGNETIC-RESONANCE, ORGANIC-MATTER, SPECTROSCOPY}, isbn = {0008-4271}, url = {://A1994NG04200001}, author = {Fox, C. A. and Preston, C. M. and Fyfe, C. A.} }