title: Acetylene dithiolate linking up the [Tp'W(CO)(CN)] moiety with Ru(II) or Pd(II.).
abstract: A series of heterodinuclear complexes with acetylene dithiolate (acdt(2-) ) as the bridging moiety were synthesised by a facile one-pot procedure that avoided use of the highly elusive acetylene dithiol. Generation of the W-Ru complex [Tp'W(CN)(CO)(C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )] (Tp'=hydrotris(3,5-dimethylpyrazolyl)borate) and the W-Pd complexes [Tp'W(CN)(CO)(C2 S2 )Pd(dppe)] and [Tp'W(CO)2 (C2 S2 )Pd(dppe)][PF6 ] (dppe=1,2-bis(diphenylphoshino)ethane), which exhibit a [W(η(2) -κ(2) -C2 S2 )M] core (M=Ru, Pd), was accomplished by using a transition-metal-assisted solvolytical removal of the Me3 Si-ethyl thiol protecting groups. All intermediate species of the reaction have been fully characterised. The highly coloured W-Ru complex [Tp'W(CN)(CO)(C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )] shows reversible redox chemistry, as does the prototype complex [Tp'W(CO)2 (C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )][PF6 ]. Single crystal X-ray diffraction and IR, EPR and UV/Vis spectroscopic studies in conjunction with DFT calculations prove the high electronic delocalisation of states over the acdt(2-) linker. Comparative studies revealed a higher donor strength and more pronounced dithiolate character of acdt(2-) in [Tp'W(CN)(CO)(C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )] relative to [Tp'W(CO)2 (C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )](+) . In addition, the influence of the overall complex charge on the metric parameters was investigated by single-crystal X-ray diffraction studies with the W-Pd complexes [Tp'WL2 (C2 S2 )Pd(dppe)] (L=(CN(-) )(CO) or (CO)2 ). The central [W(C2 S2 )Pd] units exhibit high structural similarity, which indicates the extensive delocalisation of charge over both metals.
authors.affiliation: Institut für Chemie, Universität Rostock, Albert-Einstein-Straße 3a (Germany), Fax: (+49) 381-4986380. wolfram.seidel@uni-rostock.de.
authors.forename: Wolfram W
authors.initials: WW
authors.lastname: Seidel
authors.forename: Woldemar
authors.initials: W
authors.lastname: Dachtler
authors.forename: Julia
authors.initials: J
authors.lastname: Semmler
authors.forename: Marco
authors.initials: M
authors.lastname: Tänzler
authors.forename: Manuel
authors.initials: M
authors.lastname: Folk
authors.forename: Alexander
authors.initials: A
authors.lastname: Villinger
keywords: S ligands; alkyne ligands; redox chemistry; template synthesis; through-bond interactions