title: Copper(I) and silver(I) bis(trifluoromethanesulfonyl)imide and their interaction with an arene, diverse olefins, and an NTf2(-)-based ionic liquid.
abstract: The chemistry of coinage metal bis(triflyl)imides of technological interest, CuNTf(2) and AgNTf(2), their synthesis and complexes with excess of comparatively weakly coordinating NTf(2)(-) as well as with ether, olefins, and the arene mesitylene are described. The existence of the solvent-free pure phase [CuNTf(2)](∞) has not been evidenced so far. Contrary to the literature, in which the preparation of [CuNTf(2)](∞) is supposed to be carried out by reacting mesityl copper, [Cu(Mes)](5), and HNTf(2), we found that in fact this reaction leads reproducibly to the interesting copper diarene sandwich complex [Cu(η(3)-MesH)(2)][Cu(NTf(2))(2)] (1) (MesH = 1,3,5-trimethylbenzene). The unexpectedly stable molecular etherate [Cu(Et(2)O)(NTf(2))] (2) turned out to be the best precursor for CuNTf(2) having only an inert and easily exchangeable solvent ligand. The coordination mode of NTf(2)(-) in 1 and 2 as well as in the hitherto unknown crystalline phase of [AgNTf(2)](∞) (3) is described. The complex formation, which takes place when dissolving 2 or 3 in the room temperature ionic liquid (RTIL) [emim]NTf(2) ([emim](+) = 1-ethyl-3-methylimidazolium), has been studied. Furthermore, the reaction of 1-3 towards the diolefins 1,5-cyclooctadiene (COD), 2,5-norbornadiene (NBD) and isoprene (2-methylbuta-1,3-diene) and towards ethylene has been investigated. The products 4-13 of these conversions have been isolated and fully characterized by NMR- and IR spectroscopies, mass spectrometry, and elemental- and XRD analyses. The potential of [Cu(η(3)-MesH)(2)][Cu(NTf(2))(2)] (1), [Cu(Et(2)O)(NTf(2))] (2) and [AgNTf(2)](∞) (3) as well as of [emim][M(NTf(2))(2)] (M = Cu 4, Ag 5) as chemisorbers for ethylene was studied by NMR spectroscopy.
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35032 Marburg, Germany.
authors.forename: Marion
authors.initials: M
authors.lastname: Stricker
authors.forename: Benjamin
authors.initials: B
authors.lastname: Oelkers
authors.forename: Carl Philipp
authors.initials: CP
authors.lastname: Rosenau
authors.forename: Jörg
authors.initials: J
authors.lastname: Sundermeyer
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D047250:Calixarenes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry; D007094:Imides / Q000737:chemistry; D052578:Ionic Liquids / Q000737:chemistry*; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012834:Silver / Q000737:chemistry
chemical_list: D000475:Alkenes; D006845:Hydrocarbons, Fluorinated; D007094:Imides; D052578:Ionic Liquids; D009942:Organometallic Compounds; C575299:bis(trifluoromethanesulfonyl)imide; D047250:Calixarenes; D012834:Silver; D003300:Copper