Counterintuitive solvation effect of ionic-liquid/DMSO solvents on acidic C-H dissociation and insight into
Wenzhi Luo1, Chong Mao1, Pengju Ji1
1Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University Beijing 100084 China jdyang@mail.tsinghua.edu.cn jinpei_cheng@mail.tsinghua.edu.cn.
Abstract:
How would acidic bond dissociation be affected by adding a small quantity of a weakly polar ionic liquid IL (the "apparent" or "measured" dielectric constant ε of the IL is around 10-15) into a strongly polar molecular solvent (e.g., ε of DMSO: 46.5), or vice versa? The answer is blurred, because no previous investigation was reported in this regard. Toward this, we, taking various IL/DMSO mixtures as representatives, have thoroughly investigated the effects of the respective solvent in ionic-molecular binary systems on self-dissociation of C-H acid phenylmalononitrile PhCH(CN)2 via pK a determination. As disclosed, in this category of binary media, (1) no linear correspondence exists between pK a and molar fractions of the respective solvent components; (2) only ∼1-2 mol% of weakly polar ILs in strongly polar DMSO make C-H bonds even more dissociative than in neat DMSO; (3) a small fraction of DMSO in ILs (<10 mol%) can dramatically ease acidic C-H-dissociation; and (4) while the DMSO fraction further increases, its acidifying effect becomes much attenuated. These findings, though maybe counterintuitive, have been rationalized on the basis of the precise pK a measurement of this work in relation to the respective roles of each solvent component in solvation.
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