Cyclometalation of lanthanum(iii) based MOF for catalytic hydrogenation of carbon dioxide to formate.

The hydrogenation of carbon dioxide (CO 2 ) to formic acid is of great importance due to its useful properties in the chemical industry. In this work, we have prepared a novel metal-organic framework (MOF), JMS-1, using bipyridyl dicarboxylate linkers, with molecular formula [La 2 (bpdc) 3 (DMF) 3 ] n . Network analysis of JMS-1 revealed a new 7-connected topology ( zaz ). The MOF backbone of the activated phase (JMS-1a) was functionalized by cyclometalation using [RuCl 2 ( p -cymene)] 2 to produce Ru(ii)@JMS-1a. Both JMS-1a and Ru(ii)@JMS-1a were able to convert CO 2 in the presence of hydrogen to formate. Ru(ii)@JMS-1a displayed outstanding conversion evidenced by a yield of 98% of formate under optimized conditions of total pressure 50 bar (CO 2 /H 2 = 1 : 4, temperature 110 °C, time 24 h, 5 mmol KOH, 8 mL ethanol). This work is significant in providing new strategies of incorporating active catalytic centres in MOFs for efficient and selective conversion of CO 2 to formate.