The catalytic conversion of cis-decalin was studied at a hydrogen pressure of 5.2 MPa and temperatures of 250-410 degrees C on iridium and platinum supported on non-acidic silica. The absence of catalytically active Bronsted acid sites was indicated by both FT-IR spectroscopy with pyridine as a probe and the selectivities in a catalytic test reaction, viz, the hydroconversion of n-octane. On iridium/silica, decalin hydroconversion starts at ca. 250-300 degrees C, and no skeletal isomerization occurs. The first step is rather hydrogenolytic opening of one six-membered ring to form the direct ring-opening products butylcyclohexane, 1-methyl-2-propylcyclohexane and 1,2-diethylcyclohexane. These show a consecutive hydrogenolysis, either of an endocyclic carbon-carbon bond into open-chain decanes or of an exocyclic carbon-carbon bond resulting primarily in methane and C-9 naphthenes. The latter can undergo a further endocyclic hydrogenolysis leading to open-chain nonanes. All individual C-10 and C-9 hydrocarbons predicted by this "direct ring-opening mechanism" were identified in the products generated on the iridium/silica catalysts. The carbon-number distributions of the hydrocracked products C-9- show a peculiar shape resembling a hammock and could be readily predicted by simulation of the direct ring-opening mechanism. Platinum on silica was found to require temperatures around 350-400 degrees C at which relatively large amounts of tetralin and naphthalene are formed. The most abundant primary products on Pt/silica are spiro[4.5]decane and butylcyclohexane which can be readily accounted for by the well known platinum-induced mechanisms described in the literature for smaller model hydrocarbons, namely the bond-shift isomerization mechanism and hydrogenolysis of a secondary-tertiary carbon-carbon bond in decalin. (C) 2012 Elsevier B.V. All rights reserved.