138061-92-4Relevant academic research and scientific papers
Formation of thioruthenium carbonyl clusters via a thioallyl cation complex
Choi, Nami,Kabe, Yoshio,Ando, Wataru
, p. 607 - 613 (1992)
Tetramethylallene episulfide (1a) reacts with Ru3(CO)12 to afford the oxidative addition hydride clusters Ru3(CO)10[μ-S(C=CMe2)C(Me)=CH 2](μ-H) (2) and Ru3(CO)9[μ-S(C=CMe2)C(Me)=CH 2](μ-H) (3), respectively. The structure of 2 was characterized crystallographically. The cluster 2 undergoes decarbonylation at 60°C to form 3 in 47% yield. The cluster 3 can regenerate 2 by bubbling with carbon monoxide under 1 atm of pressure at room temperature, in 80% yield. The chemical correlations leave little doubt about the structure of 3 which has a six-electron donating (μ-S)(μ-H)η2-dimethylpentadiene ligand. The reaction of 1-tert-butyl-3,3-diphenylallene 1-episulfide (1b) with Ru3(CO)12 resulted in the formation of the cluster Ru3(CO)10[2-(μ-S)-1-tert-butyl-3-phenylindene](μ-H) (5). The X-ray structure of 5 shows that intramolecular cyclization has occurred besides C-S bond cleavage. The thioallyl cation complexes 9 and 10 are the intermediates of the formation of clusters 2 and 5. Upon warming to 80-120°C, 2 and 5 were finally converted to desulfurized products 2,4-dimethyl-1,3-pentadiene (6) (quantitative) and 1-tert-butyl-3-phenylindene (7) (56%) along with thio cluster HRu5(CO) 15[2-(μ-S)-1-tert-butyl-3-phenylindene](μ4-S) (8) (30%).
