Article
Catalytic amine-borane dehydrogenation by a PCP-pincer palladium complex: A combined experimental and DFT analysis of the reaction mechanism
Author/s | Rossin, Andrea
Bottari, Giovanni Lozano Vila, Ana María Paneque Sosa, Margarita Peruzzini, Maurizio Rossi, Andrea Zanobini, Fabrizio |
Publication Date | 2013 |
Deposit Date | 2018-02-20 |
Published in |
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Abstract | Catalytic dehydrogenation of ammonia-borane (NH3·BH 3, AB) and dimethylamine borane (NHMe2·BH 3, DMAB) by the PdII complex [(tBuPCP)Pd(H 2O)]PF6 [tBuPCP = 2,6-C6H 3(CH2PtBu2)2] leads to oligomerization and formation of ... Catalytic dehydrogenation of ammonia-borane (NH3·BH 3, AB) and dimethylamine borane (NHMe2·BH 3, DMAB) by the PdII complex [(tBuPCP)Pd(H 2O)]PF6 [tBuPCP = 2,6-C6H 3(CH2PtBu2)2] leads to oligomerization and formation of spent fuels of general formula cyclo-[BH 2-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. |
Funding agencies | Ministerio de Economía y Competitividad (MINECO). España Junta de Andalucía |
Project ID. | CTQ2010- 17476
![]() 2010 CSD2007-00006 ![]() P09-FQM-4832 ![]() |
Citation | Rossin, A., Bottari, G., Lozano Vila, A.M., Paneque Sosa, M., Peruzzini, M., Rossi, A. y Zanobini, F. (2013). Catalytic amine-borane dehydrogenation by a PCP-pincer palladium complex: A combined experimental and DFT analysis of the reaction mechanism. Dalton Transactions, 42, 3533-3541. |
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