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1.
Iodine monofluorosulfate has been found to react with fluoroolefins in the absence of a solvent to give the corresponding iodo alkyl fluorosulfates by addition of ?l and ?OSO2F across the double bond. The observed products were ICF2CF2SO3F, CF3CFlCF2SO3F, and the isomer mixture ICF2CFClSO3F and ICFClCF2SO3F. Perfluorocyclobutene was unreactive. The iodine fluorosulfate used for this study was synthesized from the reactions of either I2 or RfI with ClSO3F, with both reactions being new routes to this compound. These iodo fluorocarbon fluorosulfates are novel compounds and were characterized by spectroscopy and by formation of the derivatives CF3CFICFO and ICF2CFO. 相似文献
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Toy and Stringham recently reported [1] the synthesis of N2F+5 (CF3)3CO-, a salt containing the novel pentafluorohydrazinium cation. This cation would be of significant academic and practical interest [2] since it would constitute the first known example of a substituted NF+4 cation, i.e. an NF+4 cation in which a fluorine ligand is replaced by an NF2 group. According to the authors of [1], N2F+5(CF3)3CO- was formed in a very unusual reaction involving the transfer of a fluorine cation from (CF3)3COF to N2F4 according to: 相似文献
4.
Haiges R Vij A Boatz JA Schneider S Schroer T Gerken M Christe KO 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(2):508-517
The highly explosive molecules As(N(3))(3) and Sb(N(3))(3) were obtained in pure form by the reactions of the corresponding fluorides with (CH(3))(3)SiN(3) in SO(2) and purification by sublimation. The crystal structures and (14)N NMR, infrared, and Raman spectra were determined, and the results compared to ab initio second-order perturbation theory calculations. Whereas Sb(N(3))(3) possesses a propeller-shaped, pyramidal structure with perfect C(3) symmetry, the As(N(3))(3) molecule is significantly distorted from C(3) symmetry due to crystal packing effects. 相似文献
5.
Christe KO Wilson WW Petrie MA Michels HH Bottaro JC Gilardi R 《Inorganic chemistry》1996,35(17):5068-5071
The infrared and Raman spectra of the NH(4)(+), K(+), and Cs(+) salts of N(NO(2))(2)(-) in the solid state and in solution have been measured and are assigned with the help of ab initio calculations at the HF/6-31G and MP2/6-31+G levels of theory. In agreement with the variations observed in the crystal structures, the vibrational spectra of the N(NO(2))(2)(-) anion are also strongly influenced by the counterions and the physical state. Whereas the ab initio calculations for the free N(NO(2))(2)(-) ion indicate a minimum energy structure of C(2) symmetry, Raman polarization measurements on solutions of the N(NO(2))(2)(-) anion suggest point group C(1) (i.e., no symmetry). This is attributed to the very small (<3 kcal/mol) N-NO(2) rotational barrier in N(NO(2))(2)(-) which allows for easy deformation. 相似文献
6.
Lehmann JF Schrobilgen GJ Christe KO Kornath A Suontamo RJ 《Inorganic chemistry》2004,43(22):6905-6921
The single-crystal X-ray structures of [XF(6)][Sb(2)F(11)] (X = Cl, Br, I) have been determined and represent the first detailed crystallographic study of salts containing the XF(6)(+) cations. The three salts are isomorphous and crystallize in the monoclinic space group P2(1)/n with Z = 4: [ClF(6)][Sb(2)F(11)], a = 11.824(2) A, b = 8.434(2) A, c = 12.088(2) A, beta = 97.783(6) degrees , V = 1194.3(4) A(3), R(1) = 0.0488 at -130 degrees C; [BrF(6)][Sb(2)F(11)], a = 11.931(2) A, b = 8.492(2) A, c = 12.103(2) A, beta = 97.558(4) degrees , V = 1215.5(4) A(3), R(1) = 0.0707 at -130 degrees C; [IF(6)][Sb(2)F(11)], a = 11.844(1) A, b = 8.617(1) A, c = 11.979(2) A, beta = 98.915(2) degrees , V = 1207.8(3) A(3), R(1) = 0.0219 at -173 degrees C. The crystal structure of [IF(6)][Sb(2)F(11)] was also determined at -100 degrees C and was found to crystallize in the monoclinic space group P2(1)/m with Z = 4, a = 11.885(1) A, b = 8.626(1) A, c = 12.000(1) A, beta = 98.44(1), V = 1216.9(2) A(3), R(1) = 0.0635. The XF(6)(+) cations have octahedral geometries with average Cl-F, Br-F, and I-F bond lengths of 1.550(4), 1.666(11) and 1.779(6) [-173 degrees C]/1.774(8) [-100 degrees C] A, respectively. The chemical shifts of the central quadrupolar nuclei, (35,37)Cl, (79,81)Br, and (127)I, were determined for [ClF(6)][AsF(6)] (814 ppm), [BrF(6)][AsF(6)] (2080 ppm), and [IF(6)][Sb(3)F(16)] (3381 ppm) in anhydrous HF solution at 27 degrees C, and spin-inversion-recovery experiments were used to determine the T(1)-relaxation times of (35)Cl (1.32(3) s), (37)Cl (2.58(6) s), (79)Br (24.6(4) ms), (81)Br (35.4(5) ms), and (127)I (6.53(1) ms). Trends among the central halogen chemical shifts and T(1)-relaxation times of XF(6)(+), XO(4)(-), and X(-) are discussed. The isotropic (1)J-coupling constants and reduced coupling constants for the XF(6)(+) cations and isoelectronic hexafluoro species of rows 3-6 are empirically assessed in terms of the relative contributions of the Fermi-contact, spin-dipolar, and spin-orbit mechanisms. Electronic structure calculations using Hartree-Fock, MP2, and local density functional methods were used to determine the energy-minimized gas-phase geometries, atomic charges, and Mayer bond orders of the XF(6)(+) cations. The calculated vibrational frequencies are in accord with the previously published assignments and experimental vibrational frequencies of the XF(6)(+) cations. Bonding trends within the XF(6)(+) cation series have been discussed in terms of natural bond orbital (NBO) analyses, the ligand close-packed (LCP) model, and the electron localization function (ELF). 相似文献
7.
Roland A. Bougon Karl O. Christe William W. Wilson 《Journal of fluorine chemistry》1985,30(2):237-239
Evidence is presented for the existence of (O2+)2MF62?(M=Ni,Mn) salts. These salts are marginally stable up to about 10°C and are characterized by an OO stretching frequency of about 1805 cm?1. 相似文献
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Karl O. Christe David A. Dixon Mathias Hopfinger Thomas M. Klapötke Burkhard Krumm 《Journal of fluorine chemistry》2010,131(7):791-422
The [((C6H5)3P)2N]+, [(C6H5)4P]+ and [N(CH3)4]+ salts of SeF5−, SeF62− and SeOF3− and CsSeO2F were prepared and characterized. Crystal structures were obtained for [((C6H5)3P)2N][SeF5] and [((C6H5)3P)2N][SeOF3] CH2Cl2. In contrast to oxygen-bridged dimeric TeOF3−, the SeOF3− anion in [((C6H5)3P)2N][SeOF3] CH2Cl2 is monomeric and represents the first experimentally well determined molecular structure of a monomeric trifluoro-chalcogenite anion. Similarly, [((C6H5)3P)2N][SeF5] represents the first example of a structure containing a well-isolated undistorted SeF5− anion. The NMR and the vibrational spectra and their assignments were re-examined and corrected by comparison with high-level theoretical calculations. Whereas the previously published normal coordinate analysis of SeF5− is correct, that for SeOF3− needs major revision. 相似文献