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• W2034144094 abstract "Ionic and covalent derivatives of the chlorine analogue of the nonbasic, weakly coordinating triflate ion, Cl3CSO3- or “trichlate” ion, have been prepared and compared with the corresponding more strongly coordinated chloroacetates, ClxCH3-xCO2M (x = 1−3), using 35Cl NQR (nuclear quadrupole resonance) spectroscopy. The 35Cl NQR frequencies of all types of derivatives are sensitive to the nature of the metal ion or Lewis acid and are most sensitive in the case of monochloroacetates. In covalent (including zirconocene) derivatives, the average NQR frequencies fall as the Pauling electronegativity of M falls. The results for ionic derivatives contrast with previous results for ionic hexachlorometalates: the average 35Cl NQR frequencies drop sharply as the ionic radius of the group 1 cation increases. Ab initio Gaussian 98 computations at the B3LYP/6-311++G(3df,3pd) level on isolated XCH2CO2M (M = Li, Na, K; X = F, Cl) molecules duplicate this trend, showing increasing polarization of the C−Cl bond and smaller electric field gradients for larger group 1 ions; the relevance of this to the solid state polymerization of chloroacetates (Herzberg, O.; Epple, M. Eur. J. Inorg. Chem. 2001, 1395−1406) is discussed. We have prepared the dihydrate and monohydrate of trichlic acid, Cl3CSO3H. Although trichlates have the highest average NQR frequencies of any of these salts, the NQR frequencies of trichlic acid dihydrate are anomalously lower than those of trichloroacetic acid, which suggests that it is a strong acid, ionized in the solid state to H5O2+ and Cl3CSO3- ions." @default.
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• W2034144094 date "2004-02-13" @default.
• W2034144094 modified "2023-10-10" @default.
• W2034144094 title "The Weakly Coordinating Trichloromethanesulfonate Anion: NQR Comparison of Its Coordinating Abilities via Oxygen with Those of the Chloroacetate Ions" @default.
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• W2034144094 doi "https://doi.org/10.1021/ic020727j" @default.
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