The First (Ferrocenylmethyl)imidazolium and (Ferrocenylmethyl)triazolium Room Temperature Ionic Liquids

摘要

N-(Ferrocenylmethyl)imidazo!e (3a),1-(ferrocenylmethyl)-1,2,4-triazole (3b),1,1'bis[(1H-imidazol-1-yl)methyl]ferrocene (8a),1,1/-bis{[1H-(2-methyl)imidazol-1-yl]methyl]ferrocene (8b),and 1,1'-bisKIH-1,2,4-triazol-l-yl)methyl]ferrocene (8c) were synthesized in moderate yields.These compounds were quaternized with methyl iodide to form 1-(ferrocenylmethyl)-3-methylimidazolium iodide (4a),1-(ferrocenylmethyl)-4-methyl-1,2,4-triazolium iodide (4b),1,1'-bis{[1-(2,3-dimethyl)imidazolium]methyl}ferrocene diiodide (9b),and 1,1/-bis{[1-(4-methyl)-1,2,4-triazolium]methyl}-ferrocene diiodide (9c),respectively,in excellent yields.Compounds 4a,4b,9b,and 9c were metathesized with bis(trifluoromethanesulfonyl)amide to give high yields of 5a,5b,10b,and 10c.With potassium hexafluorophosphate,9b forms 10d.Salts 5a,5b,and 10c are the first room-temperature ionic liquids with cations containing an organometallic moiety that exhibit 7_g values well below room temperature,i.e.,-32,-16,and -11 deg C.The compounds were characterized by ~1H,~19F,and ~13C NMR,MS,and elemental analyses.T_g values and melting points were determined by DSC.T_d values (5% weight loss temperature) were recorded by TGA.X-ray single-crystal structures show that 9c and 10d crystallize in the triclinic space group P1.