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Issue 10, 2013
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Catalytic amine-borane dehydrogenation by a PCP-pincer palladium complex: a combined experimental and DFT analysis of the reaction mechanism

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Abstract

Catalytic dehydrogenation of ammonia-borane (NH3·BH3, AB) and dimethylamine borane (NHMe2·BH3, DMAB) by the PdII complex [(tBuPCP)Pd(H2O)]PF6 [tBuPCP = 2,6-C6H3(CH2PtBu2)2] leads to oligomerization and formation of spent fuels of general formula cyclo-[BH2–NR2]n (n = 2,3; R = H, Me) as reaction byproducts, while one equivalent of H2 is released per amine-borane equivalent. The processes were followed through multinuclear (31P, 1H, 11B) variable temperature NMR spectroscopy; kinetic measurements on the hydrogen production rate and the relative rate constants were also carried out. One non-hydridic intermediate could be detected at low temperature, whose chemical nature was explored through a DFT modeling of the reaction mechanism, at the M06//6-31+G(d,p) computational level. The computational output was of help to propose a reliable mechanistic picture of the process.

Graphical abstract: Catalytic amine-borane dehydrogenation by a PCP-pincer palladium complex: a combined experimental and DFT analysis of the reaction mechanism

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Publication details

The article was received on 27 Sep 2012, accepted on 04 Dec 2012 and first published on 04 Dec 2012


Article type: Paper
DOI: 10.1039/C2DT32273K
Citation: Dalton Trans., 2013,42, 3533-3541
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    Catalytic amine-borane dehydrogenation by a PCP-pincer palladium complex: a combined experimental and DFT analysis of the reaction mechanism

    A. Rossin, G. Bottari, A. M. Lozano-Vila, M. Paneque, M. Peruzzini, A. Rossi and F. Zanobini, Dalton Trans., 2013, 42, 3533
    DOI: 10.1039/C2DT32273K

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