High ethene/ethane selectivity in 2,2'-bipyridine-based silver(i) complexes by removal of coordinated solvent

Angew Chem Int Ed Engl. 2015 May 4;54(19):5740-3. doi: 10.1002/anie.201500251. Epub 2015 Mar 12.

Abstract

Following removal of coordinated CH3 CN, the resulting complexes [Ag(I) (2,2'-bipyridine)][BF4 ] (1) and [Ag(I) (6,6'-dimethyl-2,2'-bipyridine)][OTf] (2) show ethene/ethane sorption selectivities of 390 and 340, respectively, and corresponding ethene sorption capacities of 2.38 and 2.18 mmol g(-1) when tested at an applied gas pressure of 90 kPa and a temperature of (20±1) °C. These ethene/ethane selectivities are 13 times higher than those reported for known solid sorbents for ethene/ethane separation. For 2, ethene sorption reached 90 % of equilibrium capacity within 15 minutes, and this equilibrium capacity was maintained over the three sorption/desorption cycles tested. The rates of ethene sorption were also measured. To our knowledge, these are the first complexes, designed for olefin/paraffin separations, which have open silver(I) sites. The high selectivities arise from these open silver(I) sites and the relatively low molecular surface areas of the complexes.

Keywords: adsorption; alkenes; coordination modes; silver; solvent effects.