Hydrogenolysis of cycloalkanes on a tantalum hydride complex supported on silica and insight into the deactivation pathway by the combined use of 1D solid-state NMR and EXAFS spectroscopies.
Hydrogenolysis of cyclic alkanes is catalysed by [(triple bond)SiO)(2)Ta-H] (1) at 160 degrees C and leads to lower alkanes and cyclic alkanes including cyclopentane. The turnover number is correlated with the number of carbon atoms of the cyclic alkanes, and therefore while cycloheptane is readily transformed, cyclopentane does not give any product (<1 %). The mechanism of ring contraction probably involves carbene de-insertion as a key carbon-carbon bond-cleavage step. The reluctance of cyclopentane to undergo hydrogenolysis was further studied: under the reaction conditions cyclopentane reacts with 1 to give the corresponding cyclopentyl derivative [(triple bond)SiO)(2)Ta-C(5)H(9)] (13), which evolves towards cyclopentadienyl derivative [(triple bond)SiO)(2)Ta(C(5)H(5))] (14) according to both solid-state NMR and EXAFS spectroscopies. This latter complex is inactive in the hydrogenolysis of alkanes, and therefore the formation of cyclopentane in the hydrogenolysis of various cyclic alkanes is probably responsible for the de-activation of the catalyst by formation of cyclopentadienyl complexes.
Rataboul
Franck
F
Laboratoire de Chimie Organométallique de Surface, UMR 9986 CNRS-ESCPE Lyon, 43 boulevard du 11 Novembre 1918, 69616 Villeurbanne Cedex, France.
Chabanas
Mathieu
M
de Mallmann
Aimery
A
Copéret
Christophe
C
Thivolle-Cazat
Jean
J
Basset
Jean-Marie
JM