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.

The reaction of [([triple bond]SiO)Zr(CH(2)tBu)(3)] with H(2) at 150 degrees C leads to the hydrogenolysis of the zirconium-carbon bonds to form a very reactive hydride intermediate(s), which further reacts with the surrounding siloxane ligands present at the surface of this support to form mainly two different zirconium hydrides: [([triple bond]SiO)(3)Zr-H] (1a, 70-80%) and [([triple bond]SiO)(2)ZrH(2)] (1b, 20-30%) along with silicon hydrides, [([triple bond]SiO)(3)SiH] and [([triple bond]SiO)(2)SiH(2)]. Their structural identities were identified by (1)H DQ solid-state NMR spectroscopy as well as reactivity studies. These two species react with CO(2) and N(2)O to give, respectively, the corresponding formate [([triple bond]SiO)(4-x)Zr(O-C(=O)H)(x)] (2) and hydroxide complexes [([triple bond]SiO)(4-x)Zr(OH)(x)] (x = 1 or 2 for 3a and 3b, respectively) as major surface complexes.