Polysulfonylamine. LXXVII. Synthese neuer Triorganoelement(IV)‐di(fluorsulfonyl)amide R₃EN(SO₂F)₂ (E = Si, Ge, Sn, Pb) und Kristallstrukturen von Me₃PbN(SO₂F)₂ und CsN(SO₂F)₂

Abstract

Inhaltsiibersicbt. Die folgenden Verbindungen wurden erstmalig undloder nach neuen Verfahren synthetisiert [Z = N(S02F)2]: Me3SiZ durch Transaminierung von HZ mit (Me3Si)2NH; Ph3SiZ (lb), Ph3SnZ (3f), Me3PbZ (4a) und Ph3PbZ (4 b) durch Metathese des entsprechenden R3ECl mit AgZ oder AgZ.C&; Me3GeZ (2), Me3SnZ, 4a und 4b durch Acidolyse von R4E mit HZ; "Hex3SnZ (3e) durch Neutralisation von "Hex3SnOH mit HZ. Bei l b , 2, 3e, 3f, 4 a und 4 b handelt es sich um neue Verbindungcn. Die Kristallstrukturen von 4 a (triklin, Raumgruppe P1) und von CsoZe (8; monoklin, Raumgruppe P21/n) wurden durch Tieftemperatur-Rontgenbeugung ermittelt. Die asymmetrische Einheit von 4 a besteht aus einem Ionenpaar Me3PboZe, das durch eine Blei-Stickstoff-Bindung und eine schwache Blei-Sauerstoff-Wechselwirkung gebildet wird

Synthesis of Poly- and the First Perfluoroalkyl-N(SO2F)2Derivatives: Improved Methods for the Preparation of XN(SO2F)2(X = H, Cl) and Single-Crystal Diffraction Studies of HN(SO2Cl)2, HN(SO2F)2, and CF3CH2N(SO2F)2

“…In covalent R−N(SO 2 F) 2 derivatives, the S−O bond distances lie in the range 1.375−1.405 Å, which is close to the S−O bond length found in SO 2 F 2 (1.405 Å), where the S−O bond order is assigned as 2.0 by Gillespie et al These S−O distances are, however, shorter than the corresponding bond lengths found in CsN(SO 2 F) 2 [1.421(3) Å], , (C 6 H 5 ) 3 XN(SO 2 F) 2 [X = C, 1.414(3) Å; X = P, 1.419(2) Å], Me 3 PbN(SO 2 F) 2 [1.418(6) Å], NH 2 (SO 3 ) - (1.457 Å), , NH(SO 3 ) 2 2- [1.449 Å], , and N(SO 3 ) 3 3- (1.468 Å) . An increase in S−O bond order is observed in going from an ionic to a covalently bonded R−N(SO 2 F) 2 derivative.…”

“…Fluorination of HN(SO 2 Cl) 2 with SbF 3 has been reported recently, but no detailed procedure is listed . We found that SbF 3 was superior to AsF 3 for the fluorination of HN(SO 2 Cl) 2 .…”

“…Although HN(SO 2 Cl) 2 and its derivatives have been known for over 3 decades, no structures with the N(SO 2 Cl) 2 moiety have been reported . There has been a recent increase in interest in the structures of compounds containing the N(SO 2 X) 2 moiety. ,,,, The modifications we have made to the synthetic procedure for the preparation of HN(SO 2 F) 2 afford this acid, as well as its fluorinated analogue in high purity. The availability of diffraction quality crystals formed at low temperatures for these acids and CF 3 CH 2 N(SO 2 F) 2 provided an opportunity to study the cryogenic crystal and molecular structures of these compounds.…”

“…More recent reports deal with some new N(SO 2 F) 2 derivatives, such as R 3 EN(SO 2 F) 2 (E = Si, , Ge, Sn, , Pb 3 ; R = alkyl), [Ph 3 C][N(SO 2 F) 2 ], [Ph 3 PH][N(SO 2 F) 2 ], and their crystal structures. The crystal structure of CsN(SO 2 F) 2 was determined independently by two groups. , Also syntheses of an azido derivative, N 3 N(SO 2 F) 2 , and the crystal structure of S[N(SO 2 F) 2 ] 2 were reported.…”

Physical and Electrochemical Properties ofN-Alkyl-N-methylpyrrolidinium Bis(fluorosulfonyl)imide Ionic Liquids: PY13FSI and PY14FSI

“…Of particular interest are a new set of ILs based upon the bis(fluorosulfonyl)imide (FSI − ), N(SO 2 F) 2 − , anion. − A variety of synthesis techniques have been reported for the FSI − anion − and crystal structures are known for LiFSI, KFSI, and CsFSI. ,, Alkali metal salts (K, Rb, Cs) with FSI − have relatively low melting points for inorganic salts and CsFSI is reported to be thermally stable to 300 °C . The IL with 1-ethyl-3-methylimidazolium cations (C 2 mimFSI) has a low melting point of −13 °C and (at 25 °C) a low viscosity of 18−25 cP and high conductivity of 15.4−16.5 mS/cm. , Unfortunately, the C 2 mim + cation is known to have a relatively low electrochemical stability (both cathodic and anodic). ,, In addition, C 2 mimFSI has a poorer thermal stability in contact with active electrode materials than N -methyl- N -propylpyrrolidinium bis(fluorosulfonyl)imide (PY 13 FSI) .…”