Effects of the long octyl chain on complex formation of nickel(ii) with dimethyl sulfoxide, methanol, and acetonitrile in ionic liquid of [C8mim][TFSA].

In the room-temperature ionic liquid (IL) of 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)amide ([C8mim][TFSA]), the complex formation of Ni2+ with molecular liquids (MLs), dimethyl sulfoxide (DMSO), methanol (MeOH), and acetonitrile (AN), has been examined using ultraviolet (UV)-visible spectroscopy. The overall stability constants log ßn, enthalpies , and entropies of the equilibria have been determined to elucidate the mechanism of complex formation. From a comparison of such thermodynamic parameters of the present [C8mim][TFSA] systems with those of the previous systems of 1-ethyl-3-methylimidazolium-based IL, [C2mim][TFSA], the effects of the octyl chain of the imidazolium cation, [C8mim]+, on the complex formation of Ni2+ with MLs have been demonstrated. In [C8mim][TFSA]-ML systems, more stable complexes are formed with MLs in the sequence of AN > DMSO ≫ MeOH. This sequence differs from that of DMSO ≫ AN > MeOH in [C2mim][TFSA]. For the AN systems, the stabilities of [Ni(an)n] in [C8mim][TFSA] are higher as compared to those in [C2mim][TFSA]. In contrast, for the DMSO systems, [Ni(dmso)n] is less stable in the IL with the longer alkyl chain than that in the IL with the shorter chain. The dependence of the alkyl chain length on the stabilities of [Ni(meoh)n] is the least significant among the three MLs. These varieties of the stabilities of Ni2+ complexes with the MLs have been interpreted from the thermodynamic parameters, together with the static interactions in the [C8mim][TFSA]-ML and [C2mim][TFSA]-ML solvents observed by means of 1H and 13C NMR, small-angle neutron scattering (SANS), and infrared (IR) with an ATR diamond prism.

Complex formation of nickel(ii) with dimethyl sulfoxide, methanol, and acetonitrile in a TFSA--based ionic liquid of [C2mim][TFSA].

The thermodynamics of complex formation of Ni2+ with molecular liquids (ML), dimethyl sulfoxide (DMSO), methanol (MeOH), and acetonitrile (AN) in the ionic liquid (IL) of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([C2mim][TFSA]) has been elucidated using ultraviolet (UV)-visible spectroscopy. X-ray structural analyses for single crystals grown from Ni2+-[C2mim][TFSA]-DMSO and -AN solutions at high ML contents have shown that six DMSO oxygen or AN nitrogen atoms coordinate with Ni2+ to form octahedral structures of [Ni(dmso)6](TFSA)2 and [Ni(an)6](TFSA)2, respectively. This is the same in the case of the Co2+ complex of [Co(dmso)6](TFSA)2. UV-visible spectroscopic experiments have revealed that the TFSA- anions that initially combine with Ni2+ in the IL are replaced with ML molecules in the IL-ML systems in three steps with increasing ML content. The electron donicities of the three MLs are larger in the order of DMSO > MeOH > AN. However, the stability of each complex does not simply depend on this order; the stability is higher in the order of [Ni(dmso)n] > [Ni(an)n] > [Ni(meoh)n]. In other words, the stability of the MeOH complexes is lower than that of the AN ones, despite the higher electron donicity of MeOH. The reasons for the order of the complex stabilities have been interpreted on the molecular scale, according to the stepwise enthalpies and entropies determined, together with the strength of the hydrogen bonding between the MLs and the imidazolium ring and the formation of MeOH clusters in [C2mim][TFSA].