215942-02-2Relevant academic research and scientific papers
Synthesis and reactivities of the indenyl-ruthenium cluster [(η5-C9H7)Ru(μ-SEt)]3: Indenyl effect in the trinuclear ruthenium cluster
Sato, Tetsu,Nishio, Masayuki,Ishii, Youichi,Yamazaki, Hiroshi,Hidai, Masanobu
, p. 99 - 108 (1998)
The triruthenium cluster with bridging ethanethiolato and indenyl ligands [(η5-C9H7)Ru(μ-SEt)]3 (2) was synthesized by heating the mononuclear indenyl complex [(η5-C9H7)Ru(SEt)(PPh3) 2] (1a) in toluene. Cluster 2 reacted with MeI to afford the S-methylated cluster [(η5-C9H7)3Ru 3(μ-SEt)2(μ-SEtMe)]I·CH2Cl 2 (4a) with high stereoselectivity through the attack of MeI on the axial SEt group from the equatorial side. The PF6- salt of the cationic cluster [(η5-C9H7)3Ru 3(μ-SEt)2(μ-SEtMe)][PF6] was further converted into the cationic carbonyl complex [(η5-C9H7)2Ru 2(μ-SEt)(CO)4][PF6] (5) by treatment with CO at 50°C. The crystal structures of 4a and 5 were determined by X-ray diffraction study. When a THF solution of 2 was allowed to contact with atmospheric pressure of CO at room temperature, the trinuclear carbonyl cluster [(η5-C9H7)3Ru 3(μ-SEt)3(μ-CO)(CO)] (6) and the dinuclear carbonyl complex [(η5-C9H7)Ru(μ-SEt)(CO)]2 (7) were obtained. The structures of 6 and 7 were also crystallographically determined. Furthermore, cluster 2 was oxidized in refluxing CHCl3 to give [(η5-C9H7)Ru(SEt)Cl]n (9). The Cp analogue of 2, [CpRu(μ-SEt)]3, failed to react with CO and CHCl3, and the hapticity change of the indenyl ligand in 2 is considered to be crucial for the initial interaction of 2 with CO and CHCl3. These reactions provide rare examples of the indenyl ligand effect in a multinuclear complex.
