Ruthenium dihydrogen complex for C-H activation: Catalytic H/D exchange under mild conditions

Martin H. G. Prechtl, M. Holscher, Y. Ben-David, N. Theyssen, D. Milstein, W. Leitner

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

Calalytic H/D-exchange reactions were Studied with [Ru(dtbpmp)(eta(2)-H-2)(H)(2)] (1) as catalyst. Under mild reaction conditions (25-75 degrees C) a wide range of arenes and olefins undergo H/D exchange with [D-6]benzene. A preference for protons at sp(2) carbons was observed with conversions Lip to >90% and significant regioselectivity in certain cases, For more reaction insights NMR-based kinetic studies were performed with naphthalene as substrate, revealing an activation energy of 15.8 kcal mol(-1) for the H/D exchange at the beta-position. Furthermore, the key steps of the reaction mechanism were investigated by means of DFT calculations for both model complexes (PMe2 donor sites) and real catalysts (PtBu2 donor sites). The calculations resulted in Gibb's free activation energies in the range of 10-16 kcal mol(-1), indicating H/D exchange at the beta-position of naphthalene to he clearly favoured over the alpha-position, Much is in full accordance with the experimental observations. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).
Original languageEnglish
JournalEuropean Journal of Inorganic Chemistry
Issue number22
Pages (from-to)3493-3500
Number of pages8
ISSN1434-1948
DOIs
Publication statusPublished - 2008
Externally publishedYes

Bibliographical note

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Keywords

  • ruthenium dihydrogen complexes H/D exchange CH activation deuteration DFT calculations molecular-orbital methods gaussian-basis sets hydride complexes thermal-decomposition iridium complexes ir(iii) complexes organic-molecules phosphine-ligands bond activation atoms li Chemistry

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