title: High-coordinate gold(I) complexes with dithiocarboxylate ligands.
abstract: Ferrocene dithiocarboxylate has been introduced into the chemistry of gold(I) and copper(I). First, a modified synthesis of piperidinium ferrocene dithiocarboxylate (1) is reported. Reaction of this reagent with [Au(tht)Cl] in the presence of different phosphines resulted in monomeric, dimeric, and polymeric structures. Although gold(I) is usually two coordinate, mainly three- and four-fold coordinated compounds were obtained by using ferrocene dithiocarboxylate as ligands. The isolated compounds are [(FcCSS)Au(PPh3)2] (2) (FcCSS = ferrocene dithiocarboxylate), [(FcCSS)Au2(dppm)2] (3) (dppm = bis(diphenylphosphino)methane), and [(FcCSS)Au(dppf)]n (4) (dppf = bis(diphenylphosphino)ferrocene) [{(FcCSS)Au}2(dppp)] (5) (dppp = bis(diphenylphosphino)propane). The FcCSS ligand shows a remarkable flexible coordination mode. It coordinates either in a monodentate, a chelating, or in a metal bridging mode. In the four gold(I) complexes 2-5 four different coordination modes of the FcCSS ligand are seen. Attempts to extend this rich coordination chemistry to other coinage metals were only partly successful. [(FcCSS)Cu(PPh3)2] (6) was obtained from the reaction of piperidinium ferrocene dithiocarboxylate with [(Ph3P)3CuCl]. (57)Fe-Mössbauer spectroscopy was performed for compounds 2-4. The spectra show isomer shifts and quadrupole splittings that are typical for diamagnetic ferrocenes.
authors.affiliation: Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT) , Engesserstrasse 15, 76131 Karlsruhe, Germany.
authors.forename: Christoph
authors.initials: C
authors.lastname: Kaub
authors.forename: Timo
authors.initials: T
authors.lastname: Augenstein
authors.forename: Thomas O
authors.initials: TO
authors.lastname: Bauer
authors.forename: Elisa
authors.initials: E
authors.lastname: Rothe
authors.forename: Lars
authors.initials: L
authors.lastname: Esmezjan
authors.forename: Volker
authors.initials: V
authors.lastname: Schünemann
authors.forename: Peter W
authors.initials: PW
authors.lastname: Roesky