Revisiting the Potential of Group VI Inorganic Precatalysts for the Ethenolysis of Fatty Acids through a Mechanochemical Approach.

The utilization of biobased feedstocks to prepare useful compounds is a pivotal trend in current chemical research. Among a varied portfolio of naturally available starting materials, fatty acids are abundant, versatile substrates with multiple applications. In this context, the ethenolysis of unsaturated fatty acid esters such as methyl oleate is an atom-economical way to prepare functional C10 olefins with a biobased footprint. Despite the existence of a variety of metathesis catalysts for the latter process, there is a lack of readily available, efficient, and inexpensive catalytic systems based on earth-abundant metals (Mo, W) whose preparation does not require sophisticated syntheses and manipulations. Here, a systematic exploration of homogeneous and heterogeneous inorganic Mo, W (oxy)halides shows that MoOCl 4 , while inactive as a homogeneous species, forms active and selective silica-supported ethenolysis precatalysts able to reach equilibrium conversion of methyl oleate within a few minutes upon activation with SnMe 4 . Such heterogeneous MoOCl 4 -based precatalysts were easily accessed through mechanochemical solvent-free procedures and found to contain, upon characterization by elemental analysis and Raman spectroscopy, isolated (≡SiO)Mo(=O)Cl 3 units or polymeric silica-supported [-O(≡SiO) n MoCl 4- n O-] m ( n = 1, 2) complexes depending on the molybdenum loading. The former isolated species exhibited a higher catalytic performance. The developed heterogeneous precatalysts could be applied to the ethenolysis of various substrates, including polyunsaturated fatty acid esters and industrial fatty acid methyl ester (FAME) mixtures from palm oil transesterification.