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.     «

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...     »

ISI Document Delivery No.: 114WY Times Cited: 0 Cited Reference Count: 26 Zhao, Zhi-Jian Moskaleva, Lyudmila V. Roesch, Notker Zhao, Zhi-Jian/C-8965-2009 International Doctorate Program NanoCat within the Bavarian Network of Excellence; Deutsche Forschungsgemeinschaft; Fonds der Chemischen Industrie We thank Profs. R. van Santen and J.A. Lercher for stimulating discussions. Z.J.Z. gratefully acknowledges financial support by the International Doctorate Program NanoCat within the Bavarian Network of Excellence. This work was supported by Deutsche Forschungsgemeinschaft and Fonds der Chemischen Industrie. We also acknowledge generous computing resources at Leibniz Rechenzentrum Munchen. 0 Academic press inc elsevier science San diego     «

ISI Document Delivery No.: 114WY Times Cited: 0 Cited Reference Count: 26 Zhao, Zhi-Jian Moskaleva, Lyudmila V. Roesch, Notker Zhao, Zhi-Jian/C-8965-2009 International Doctorate Program NanoCat within the Bavarian Network of Excellence; Deutsche Forschungsgemeinschaft; Fonds der Chemischen Industrie We thank Profs. R. van Santen and J.A. Lercher for stimulating discussions. Z.J.Z. gratefully acknowledges financial support by the International Doctorate Program NanoCat within the Bavarian Netwo...     »