Acetylene Dithiolate Linking up the [Tp %26apos; W(CO)(CN)] Moiety with Ru-II or Pd-II

作者：Seidel Wolfram W^*; Dachtler Woldemar; Semmler Julia; Taenzler Marco; Folk Manuel; Villinger Alexander

来源：Chemistry - A European Journal, 2013, 19(43): 14702-14711.

DOI：10.1002/chem.201301192

• alkyne ligands
• redox chemistry
• S ligands
• template synthesis
• through-bond interactions

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 WRu complex [Tp%26apos;W(CN)(CO)(C2S2)Ru(eta(5)-C5H5)(PPh3)] (Tp%26apos;=hydrotris(3,5-dimethylpyrazolyl)borate) and the WPd complexes [Tp%26apos;W(CN)(CO)(C2S2)Pd(dppe)] and [Tp%26apos;W(CO)(2)(C2S2)Pd(dppe)][PF6] (dppe=1,2-bis(diphenylphoshino)ethane), which exhibit a [W(eta(2)-kappa(2)-C2S2)M] core (M=Ru, Pd), was accomplished by using a transition-metal-assisted solvolytical removal of the Me3Si-ethyl thiol protecting groups. All intermediate species of the reaction have been fully characterised. The highly coloured WRu complex [Tp%26apos;W(CN)(CO)(C2S2)Ru(eta(5)-C5H5)(PPh3)] shows reversible redox chemistry, as does the prototype complex [Tp%26apos;W(CO)(2)(C2S2)Ru(eta(5)-C5H5)(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%26apos;W(CN)(CO)(C2S2)Ru(eta(5)-C5H5)(PPh3)] relative to [Tp%26apos;W(CO)(2)(C2S2)Ru(eta(5)-C5H5)(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 WPd complexes [Tp%26apos;WL2(C2S2)Pd(dppe)] (L=(CN-)(CO) or (CO)(2)). The central [W(C2S2)Pd] units exhibit high structural similarity, which indicates the extensive delocalisation of charge over both metals.

• 出版日期2013-10-18