Premium
N , N′ ‐Bis(trifluoromethylsulfonyl)oxamidates: Synthesis and Thermal, Electrochemical, Spectroscopic, and Structural Properties
Author(s) -
Sprenger Jan A. P.,
Konieczka Szymon Z.,
Brede Franziska A.,
Kerpen Christoph,
Drisch Michael,
Franz KlausDieter,
Ignat'ev Nikolai,
Reiss Guido J.,
Frank Walter,
Finze Maik
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500850
Subject(s) - chemistry , triethylamine , deprotonation , lithium (medication) , electrochemistry , raman spectroscopy , cyclic voltammetry , dilithium , inorganic chemistry , oxamide , medicinal chemistry , crystal structure , thermal stability , crystallography , organic chemistry , ion , medicine , physics , electrode , optics , endocrinology
Salts of the N , N′ ‐bis(trifluoromethylsulfonyl)oxamidate dianion ( 1 2– ) were obtained by deprotonation of the oxamide {CF 3 SO 2 NHC(O)} 2 (H 2 1 ) with triethylamine, tri‐ n ‐octylamine, 1‐methylimidazole (MIM), and lithium hydride in yields of 61–92 %. The synthesis of H 2 1 starting from oxalyl chloride and Na(NHSO 2 CF 3 ) was improved. The salts Li 2 1 , [Et 3 NH] 2 1 , [ n Oct 3 NH] 2 1 , and [HMIM] 2 1 were characterized by multinuclear NMR, IR, and Raman spectroscopy, mass spectrometry, and thermal and elemental analysis. The electrochemical stability of dianion 1 2– was studied by cyclic voltammetry on solutions of its lithium salt. The electrochemical properties are compared to those of H 2 1 . The conductivity of Li 2 1 in DME was found to be lower than those of Li[BF 4 ] and LiCF 3 SO 3 . The structures of 1 ∞ [Li 2 1· 2THF], [Et 3 NH] 2 1 , [ n Oct 3 NH] 2 1 , and [HMIM] 2 1 were studied by single‐crystal X‐ray diffraction. In the solid state, dianion 1 2– acts as a chelating ligand toward Li + and forms bifurcated hydrogen bonds with the N–H moieties of the organic cations. The discussion of selected spectroscopic and structural properties is aided by DFT calculations.