The Structure of the High Temperature Modification of Lithium Triflate (γ‐LiSO₃CF₃)

Abstract

The high temperature modification of lithium triflate (γ-LiSO 3 CF 3 ) crystallises in the orthorhombic space group Cmca with the lattice parameters a ϭ 6.3022(4), b ϭ 8.6989 (5), and c ϭ 20.1262(14) Å (synchrotron powder diffraction data, T ϭ 456 K). The crystal structure of γ-LiSO 3 CF 3 is disordered, in the cationic as well as the anionic partial structure, and exhibits double layers of triflate anions with the lipophilic CF 3 -groups facing each other.

Crystal Structure and Ionic Conductivity of Cesium Trifluoromethyl Sulfonate, CsSO3CF3

“…It should be noted that the staggered conformation of the triflate molecule is preserved. The high temperature modification of LiSO 3 CF 3 also shows severe disorder of the triflate anions [28]. Regarding recent results from temperature dependent NMR measurements of LiSO 3 CF 3 [10] and NaSO 3 CF 3 [25], an isotropic reorientation of the triflate anion around the center of gravity can be assumed not just for the lithium and the sodium salts but also for the cesium salt.…”

Crystal structures of the trifluoromethyl sulfonates M(SO3CF3)2 (M = Mg, Ca, Ba, Zn, Cu) from synchrotron X-ray powder diffraction data

“…Data reduction on the high-resolution powder diffraction patterns was performed using GUFI (Dinnebier & Finger, 1998). Indexing with ITO (Visser, 1969) led to rhombohedral unit cells for Ca-, Mg 0.96 Na 0.08 -and Zn-trifluoromethyl sulfonate, to an I(C)-centred monoclinic unit cell for Ba-trifluoromethyl sulfonate, and to a triclinic unit cell for Cu-trifluoromethyl sulfonate with lattice parameters given in Table 1.…”

“…In spite of the general importance of trifluoromethyl sulfonates, the crystal chemistry of the alkali metal trifluoromethyl sulfonates has been revealed only recently. Owing to the various structural phase transitions, no untwinned single crystals were available except for sodium (Sofina et al, 2003) and potassium trifluoromethyl sulfonate (Korus & Jansen, 2001), and the crystal structures had to be solved using powder diffraction data (Tremayne et al, 1992;Dinnebier et al, 2004;. In addition to these structural studies, the dynamics of anions as well as cations, and their interactions, have been investigated by two independent probes, impedance spectroscopy and solid-state NMR (van Wü llen et al, 2004(van Wü llen et al, , 2005.…”

Rational Optimization of Lewis‐Acid Catalysts for the Direct Amination of Alcohols, Part 1 – Activity Descriptors for Metal Triflates and Triflimides

“…The 3D structure of a large series of M(OTf) n and M(NTf 2 ) n salts was optimized at the BP86‐D3(BJ)/def2‐SVP level, while the electronic energy was estimated at the B3LYP‐D3(BJ)/def2‐TZVP level using the method previously reported for Al(OTf) 3 (see Computational Details in SI) . At this level of theory, triflates behaved as bidentate ligands in all structures with two O atoms coordinated to the metal cation (Figure , Figures S5–S9), matching earlier studies . The case of triflimides was more challenging, since this anion could coordinate to the metal cation either via N or O atoms (see SI for a complete discussion on this point, Figures S10–S15, Tables S2–S3) …”

“…However, for this reaction, as for other LA‐catalyzed reactions, the choice of the catalyst encompasses a narrow selection of metal salts with scarce attempts for a rationale . Another caveat is that M(OTf) n and M(NTf 2 ) n salts are usually poorly characterized (only few XRD structures are available, ) and often contain an important amount of water. For these reasons, robust descriptors are required for predicting the catalytic properties of M(OTf) n and M(NTf 2 ) n salts.…”