Stuffing Your Struts

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Science  26 Aug 2011:
Vol. 333, Issue 6046, pp. 1072-1073
DOI: 10.1126/science.333.6046.1072-d

The potential for using metal-organic frameworks (MOFs) as catalysts is often frustrated by a fundamental tradeoff. The synthetic routes for making MOFs tend to saturate all of the coordination sites of metals, even ones contained within the linkers or struts, but catalysis by metals is usually enabled by the presence of unsaturated sites. Shultz et al. developed a strategy that addresses this dilemma for metallosalen struts to use as catalysts within MOFs. Although Mn(salen) can be incorporated into MOFs for asymmetric epoxidations, other metals, such as Co(salen) for asymmetric ring opening, are unsaturated and do not form MOFs directly. The authors describe how Mn(salen) MOFs (in which zinc ions link the struts in a paddlewheel arrangement) can be demetalated with H2O2 and replaced isostructurally with a wide variety of dicationic transition-metal ions, including Co, Cr, Cu, Zn, and reduced Mn (which recovered its catalytic activity after reoxidation).

J. Am. Chem. Soc. 133, 10.1021/ja204820d (2011).

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