> Detailanzeige

Holdt, Hans‐Jürgen; Müller, Holger; Pötter, Matthias; Kelling, Alexandra; Schilde, Uwe; Starke, Ines; Heydenreich, Matthias; Kleinpeter, Erich

The First Sandwich Complex with an Octa(thioether) Coordination Sphere: Bis(maleonitrile‐tetrathia‐12‐crown‐4)silver(I)

Literatur-
verwaltung

Zur
Merkliste

Lösche von
Merkliste

Per Whatsapp teilen

Schließen

Merkliste



Sie können Bookmarks mittels Listen verwalten, loggen Sie sich dafür bitte in Ihr SLUB Benutzerkonto ein.
  • Medientyp: E-Artikel
  • Titel: The First Sandwich Complex with an Octa(thioether) Coordination Sphere: Bis(maleonitrile‐tetrathia‐12‐crown‐4)silver(I)
  • Beteiligte: Holdt, Hans‐Jürgen; Müller, Holger; Pötter, Matthias; Kelling, Alexandra; Schilde, Uwe; Starke, Ines; Heydenreich, Matthias; Kleinpeter, Erich
  • Erschienen: Wiley, 2006
  • Erschienen in: European Journal of Inorganic Chemistry, 2006 (2006) 12, Seite 2377-2384
  • Sprache: Englisch
  • DOI: 10.1002/ejic.200501109
  • ISSN: 1099-0682; 1434-1948
  • Schlagwörter: Inorganic Chemistry
  • Entstehung:
  • Anmerkungen:
  • Beschreibung: AbstractThe new tetrathiacrown ethers maleonitrile‐tetrathia‐12‐crown‐4 (mn12S4) and maleonitrile‐tetrathia‐13‐crown‐4 (mn13S4) have been prepared and characterised by X‐ray crystallographic analysis. These crown ethers form 2:1, 3:2 and 1:1 complexes with AgY (Y = BF4, PF6). The crystal structures of [Ag(mn12S4)2]BF4 (3a), [Ag(mn13S4)2]BF4 (4a) and [Ag2(mn13S4)3](PF6)2 (6b) have been determined. Compound 3a contains the centrosymmetric sandwich complex cation [Ag(mn12S4)2]+ where each mn12S4 ligand is coordinated to the Ag centre in an endo manner through all four S atoms. The 2:1 complex [Ag(mn12S4)2]+ is the first sandwich complex with a tetrathiacrown ether and the first complex with an octa(thioether) coordination sphere. The crystal structure of compound 4a also reveals a 2:1 complex. This complex, [Ag(mn13S4)2]+, exhibits a half‐sandwich structure. One mn13S4 ligand coordinates to Ag+ by all four S donor atoms and the other 13S4 crown by only one S atom. Compound 6b contains a dinuclear Ag complex. The Ag complexes 3a,b–8a,b were also studied by electrospray ionisation mass spectrometry. Collision‐induced dissociation (CID) was used to compare the relative stability of 2:1 complexes [AgL2]+ and 1:1 complexes [AgL]+ (L = mn12S4, mn13S4). The 13C NMR chemical shifts of 2:1 and 1:1 Ag complexes and their corresponding free ligands were also estimated and compared. The free energy of the barrier of ring inversion (ΔG‡) for [Ag(mn12S4)2]+ was determined to be 64 kJ mol–1. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)