Activation of Methyltrioxorhenium for Olefin Metathesis in a Zirconium-Based Metal–Organic Framework

The zirconium nodes of the metal-organic framework (MOF) known as NU-1000 serve as competent supports for the activation of methyltrioxorhenium (MTO) toward olefin metathesis. Itself inactive for olefin metathesis, MTO becomes an active catalyst only when immobilized on the strongly acidic Lewis acid sites of dehydrated NU-1000. Uptake of MTO at the dehydrated secondary building units (SBUs) occurs rapidly and quantitatively to produce a catalyst active in both gas- and liquid-phase processes. These results demonstrate for the first time the utility of MOF SBUs for olefin metathesis, an academically and industrially relevant transformation.