An equilibrated mixture of pentene isomers was produced by dehydroisomerization of n-pentane on catalysts consisting of Pt clusters within [Fe]ZSM-5 channels. These catalysts showed high isomerization rates, excellent stability even without added H-2, and isopentene selectivities above 60%. Metal sites on Pt clusters dehydrogenate n-alkanes and n-alkenes formed undergo skeletal rearrangements with high selectivity on weak acid sites prevalent in Na-[Fe]ZSM-5 after reduction of exchanged Pt cations. Zeolite channels inhibit side reactions and sintering processes that cause rapid deactivation on unprotected Pt clusters. (c) 2008 Elsevier Inc. All rights reserved.