With periodic density functional theory calculations, we examined the ring opening of methylcyclopentane to n-hexane via an alpha gamma-adsorbed metallacyclobutane intermediate over the stepped model surface Pt(322). The crucial barrier of C-C scission along this pathway was calculated as low as 79 kJ mol(-1), that is, about 20 kJ mol(-1) lower than the value for analogous steps via alpha alpha beta beta-adsorbed intermediates on the way to 2- or 3-methylpentane on Pt(211). Thus, at step sites of Pt surfaces, formation of (unbranched) n-hexane seems to be more favorable than formation of branched hexanes. (C) 2012 Elsevier Inc. All rights reserved.
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With periodic density functional theory calculations, we examined the ring opening of methylcyclopentane to n-hexane via an alpha gamma-adsorbed metallacyclobutane intermediate over the stepped model surface Pt(322). The crucial barrier of C-C scission along this pathway was calculated as low as 79 kJ mol(-1), that is, about 20 kJ mol(-1) lower than the value for analogous steps via alpha alpha beta beta-adsorbed intermediates on the way to 2- or 3-methylpentane on Pt(211). Thus, at step sites o...
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