573970-28-2Relevant academic research and scientific papers
Synthesis of the first non-carbonyl cisoid fulvalene complexes with and Ru-Ru bond bridged by thiolate ligands
Watanabe, Masanobu,Sato, Masaru,Kai, Masahiro
, p. 651 - 658 (2003)
The addition of PPh3 to a solution which was produced by the oxidation of [(η5-Cp)Ru(μ2-η6:η6-C 10H8)Ru(η5-Cp)]2+- (BF4-)2 (1) with p-benzoquinone and BF3·OEt2 (abbreviated as p-Bq/BF3) in CH2Cl2-CH3CN and subsequent Zn-reduction gave the transoid Ru-Fv complex (Fv = fulvalene) formulated as [(CH3CN)2(PPh3)Ru(μ2- η5:η5-C10H8) Ru(PPh3)(CH3CN)2]2+ (BF4-)2 (2a) in high yield as stable yellow crystals. Treatment of 2a with excess aryl thiols (ArSH; Ar = C6H5, p-CH3C6H4 and p-ClC6H4), their thiolates and aryl dithiols (1,2-benzenedithiol or 3,4-toluenedithiol) or their dithiolates at room temperature afforded the Ru-Fv complexes bridged by thiolate ligands formulated as [(PPh3)Ru(μ2-η5:η5- C10H8) (μ2-SAr)2Ru(PPh3)]2+ (BF4-)2 (3a-c), (ArS)Ru(μ2-η5:η5-C10 H8)(μ2-SAr)2Ru(SAr) (4a-c) and [(PPh3)Ru(μ2-η5:η5- C10H8) (μ2-S2C6H3R) Ru(PPh3)]2+(BF4-)2 (5a; R = H, 5b; R = CH3), in high yield, respectively. Treatment of 2a with excess tert-butylthiolate produced the complex [(PPh3)Ru(μ2-η5:η5- C10H8) (μ2-StBu)2Ru]2+ (BF4-)(StBu-) (6a). In contrast with complexes 2-5, a coordinatively unsaturated Ru atom was found in 6a, which is probably formed owing to the bulkiness of the tBuS- ligand. X-Ray analysis of complexes 3-6 showed the presence of an RuIII-RuIII single bond.
