Metathesis of Alkanes Catalyzed by Silica-Supported Transition Metal Hydrides

The silica-supported transition metal hydrides (=Si-O-Si=)(=Si-O-)2Ta-H and (=Si-O-)xM-H (M, chromium or tungsten) catalyze the metathesis reaction of linear or branched alkanes into the next higher and lower alkanes at moderate temperature (25degrees to 200degreesC). With (=Si-O-Si=)(=Si-O-)2Ta-H, ethane was transformed at room temperature into an equimolar mixture of propane and methane. Higher and lower homologs were obtained from propane, butane, and pentane as well as from branched alkanes such as isobutane and isopentane. The mechanism of the step leading to carbon-carbon bond cleavage and formation likely involves a four-centered transition state between a tantalum-alkyl intermediate and a carbon-carbon final sigma-bond of a second molecule of alkane.