RESUMEN
A simple, one-step mechanochemical procedure for immobilisation of homogeneous metathesis catalysts in metal-organic frameworks was developed. Grinding MIL-101-NH2 (Al) with a Hoveyda-Grubbs second-generation catalyst resulted in a heterogeneous catalyst that is active for metathesis and one of the most stable immobilised metathesis catalysts. During the mechanochemical immobilisation the MIL-101-NH2 (Al) structure was partially converted to MIL-53-NH2 (Al). The Hoveyda-Grubbs catalyst entrapped in MIL-101-NH2 (Al) is responsible for the observed catalytic activity. The developed synthetic procedure was also successful for the immobilisation of a Zhan catalyst.
RESUMEN
The desire to utilise biobased feedstocks and develop more sustainable chemistry poses new challenges in catalysis. A synthetically useful catalytic conversion is ethenolysis, a cross metathesis reaction with ethylene. In this Review, the state of the art of ethenolysis in biobased chemistry was extensively examined using methyl oleate as a model compound for fatty acids. Allied to this, the ethenolysis of fatty acid, polymers and more challenging substrates are reviewed. To determine the limiting factors for the application of ethenolysis on biomass, the influence of reaction parameters were investigated and the bottlenecks for reaching high turnover numbers identified.