A Multivariate 2D Metal-Organic Framework with Open Metal Sites for Catalytic CO 2 Cycloaddition and Cyanosilylation Reactions.

This work reports the synthesis of a dual functional 2D framework, {[Zn ₂ (4-tpom) ₂ (oxdz) ₂ ]·4H ₂ O} _n ( 1 ), at room temperature, where a bent dicarboxylate, oxdz ^2- (4,4'-(1,3,4-oxadiazole-2,5-diyl)dibenzoate), and a neutral flexible N-donor linker, 4-tpom (tetrakis(4-pyridyloxymethylene)methane), are utilized. Its single-crystal X-ray analysis indicated a 2-fold interpenetrated 2D framework having tetracoordinated Zn(II) centers and dangling pyridyl groups. Its further characterization was carried out with elemental microanalysis, FTIR spectroscopy, TG analysis, and powder X-ray diffraction. The tetracoordinated Zn(II) centers as active Lewis acidic sites and the N atoms of 4-tpom as Lewis basic sites in 1 are explored for its functioning as a heterogeneous catalyst in two important reactions, (i) cycloaddition of CO ₂ with various epoxides and (ii) cyanosilylation reaction under solvent-free conditions. We could successfully show the cycloaddition of styrene oxide with CO ₂ (99% conversion) under balloon pressure with low catalyst (0.2-0.3 mol %) and cocatalyst (0.5-0.75 mol %) loadings, which is otherwise difficult to achieve. It was observed that all the substrates (aromatic and aliphatic), irrespective of their sizes, showed conversion percentage >99%. In the cyanosilylation reaction, a conversion of 96% was obtained with 1.5 mol % of 1 at room temperature for 12 h. This framework emerged as an excellent recyclable catalyst for both the reactions.