Acetylene Dithiolate Linking up the [Tp′W(CO)(CN)] Moiety with RuII or PdII. Issue 43 (11th September 2013)

• Record Type: Journal Article
• Authors: Seidel, Wolfram W.; Dachtler, Woldemar; Semmler, Julia; Tänzler, Marco; Folk, Manuel; Villinger, Alexander
• Is Part Of: Chemistry. Volume 19:Issue 43(2013)
• Page Start: 14702
• Page End: 14711
• Publication Date: 2013-09-11
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201301192
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A series of heterodinuclear complexes with acetylene dithiolate (acdt<sup>2−</sup>) 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)(C<sub>2</sub>S<sub>2</sub>)Ru(η<sup>5</sup>‐C<sub>5</sub>H<sub>5</sub>)(PPh<sub>3</sub>)] (Tp'=hydrotris(3, 5‐dimethylpyrazolyl)borate) and the W–Pd complexes [Tp′W(CN)(CO)(C<sub>2</sub>S<sub>2</sub>)Pd(dppe)] and [Tp′W(CO)<sub>2</sub>(C<sub>2</sub>S<sub>2</sub>)Pd(dppe)][PF<sub>6</sub>] (dppe=1, 2‐bis(diphenylphoshino)ethane), which exhibit a [W(η<sup>2</sup>‐κ<sup>2</sup>‐C<sub>2</sub>S<sub>2</sub>)M] core (M=Ru, Pd), was accomplished by using a transition‐metal‐assisted solvolytical removal of the Me<sub>3</sub>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)(C<sub>2</sub>S<sub>2</sub>)Ru(η<sup>5</sup>‐C<sub>5</sub>H<sub>5</sub>)(PPh<sub>3</sub>)] shows reversible redox chemistry, as does the prototype complex [Tp′W(CO)<sub>2</sub>(C<sub>2</sub>S<sub>2</sub>)Ru(η<sup>5</sup>‐C<sub>5</sub>H<sub>5</sub>)(PPh<sub>3</sub>)][PF<sub>6</sub>]. 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<sup>2−</sup> linker. Comparative studies revealed a higher donor strength and more pronounced dithiolate character of acdt<sup>2−</sup> in [Tp′W(CN)(CO)(C<sub>2</sub>S<sub>2</sub>)Ru(η<sup>5</sup>‐C<sub>5</sub>H<sub>5</sub>)(PPh<sub>3</sub>)] relative to [Tp′W(CO)<sub>2</sub>(C<sub>2</sub>S<sub>2</sub>)Ru(η<sup>5</sup>‐C<sub>5</sub>H<sub>5</sub>)(PPh<sub>3</sub>)]<sup>+</sup>. 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′WL<sub>2</sub>(C<sub>2</sub>S<sub>2</sub>)Pd(dppe)] (L=(CN<sup>−</sup>)(CO) or (CO)<sub>2</sub>). The central [W(C<sub>2</sub>S<sub>2</sub>)Pd] units exhibit high structural similarity, which indicates the extensive delocalisation of charge over both metals.</p> </abstract>