Synthesis and characterization of ionic liquids containing copper, manganese, or zinc coordination cations

Copper-, manganese-, and zinc-based ionic liquids (Cu{NH(2)CH(2)CH(2)OH}(6)[CH(3)(CH(2))(3)CH(C(2)H(5))CO(2)](2) (2), Cu{NH(CH(2)CH(2)OH)(2)}(6)[CH(3)(CH(2))(3)CH(C(2)H(5))CO(2)](2) (3A), Cu{NH(CH(2)CH(2)OH)(2)}(6)[CF(3)SO(3)](2) (3B), Cu{NH(CH(2)CH(2)OH)(2)}(6)[(CF(3)SO(2))(2)N](2) (3C), Mn{NH(CH(2)CH(2)OH)(2)}(6)[CF(3)SO(3)](2) (4), and Zn{NH(2)CH(2)CH(2)OH}(6)[CF(3)SO(3)](2) (5)) are synthesized in a single-step reaction. Infrared data suggest that ethanolamine preferentially coordinates to the metal center through the amine group in 2 and the hydroxyl group in 5. In addition, diethanolamine coordinates through the amine group in 3A, 3C, and 4 and the hydroxyl group in 3B. The compounds are viscous (>1000 cP) at room temperature, but two (3C and 4) display specific conductivities that are reasonably high for ionic liquids (>20 mS cm(-1)). All of the compounds display a glass transition (T(g)) below -50 °C. The cyclic voltammograms (CVs) of 2, 3A, 3B, and 3C display a single quasi-reversible wave associated with Cu(II)/Cu(I) reduction and re-oxidation while 5 shows a wave attributed to Zn(II)/Zn(0) reduction and stripping (re-oxidation). Compound 4 is the first in this new family of transition metal-based ionic liquids (MetILs) to display reversible Mn(II)/Mn(III) oxidation and re-reduction at 50 mV s(-1) using a glassy carbon working electrode.