Probing the second dehydrogenation step in ammonia-borane dehydrocoupling: characterization and reactivity of the key intermediate, B-(cyclotriborazanyl)amine-borane

Kalviri, Hassan A.; Gärtner, Felix; Ye, Gang; Korobkov, Ilia; Baker, R. Tom

doi:10.1039/c4sc02710h

Title: Probing the second dehydrogenation step in ammonia-borane dehydrocoupling: characterization and reactivity of the key intermediate, B-(cyclotriborazanyl)amine-borane

Journal Article · Thu Oct 30 00:00:00 EDT 2014 · Chemical Science

DOI:https://doi.org/10.1039/c4sc02710h· OSTI ID:1624910

Kalviri, Hassan A. ^[1]; Gärtner, Felix ^[2]; Ye, Gang ^[1]; Korobkov, Ilia ^[1]; Baker, R. Tom ^[1]

Univ. of Ottawa, ON (Canada). Dept. of Chemistry. Centre for Catalysis Research and Innovation (CCRI)
Univ. of Ottawa, ON (Canada). Dept. of Chemistry. Centre for Catalysis Research and Innovation (CCRI); Leibniz Inst. for Catalysis (LIKAT), Rostock (Germany)

While thermolysis of ammonia-borane (AB) affords a mixture of aminoborane- and iminoborane oligomers, the most selective metal-based catalysts afford exclusively cyclic iminoborane trimer (borazine) and its B–N cross-linked oligomers (polyborazylene). This catalysed dehydrogenation sequence proceeds through a branched cyclic aminoborane oligomer assigned previously as trimeric B-(cyclodiborazanyl)amine-borane (BCDB). Herein we utilize multinuclear NMR spectroscopy and X-ray crystallography to show instead that this key intermediate is actually tetrameric B-(cyclotriborazanyl)amine-borane (BCTB) and a method is presented for its selective synthesis from AB. The reactivity of BCTB upon thermal treatment as well as catalytic dehydrogenation is studied and discussed with regard to facilitating the second dehydrogenation step in AB dehydrocoupling.

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Research Organization:: Univ. of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: FC36-05GO15051

OSTI ID:: 1624910

Journal Information:: Chemical Science, Vol. 6, Issue 1; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 48 works

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Amino olefin nickel(I) and nickel(0) complexes as dehydrogenation catalysts for amine boranes Vogt, M.; De Bruin, B.; Berke, H. Royal Society of Chemistry https://doi.org/10.5167/uzh-60403	text	January 2011
The hydrogen economy Crabtree, George W.; Dresselhaus, Mildred S.; V. Buchanan, And Michelle IEEE Engineering Management Review, Vol. 34, Issue 4 https://doi.org/10.1109/emr.2006.261397	journal	January 2006
Development of Rhenium Catalysts for Amine Borane Dehydrocoupling and Transfer Hydrogenation of Olefins Jiang, Y.; Blacque, O.; Frech, C. M. American Chemical Society https://doi.org/10.5167/uzh-21033	text	January 2009
High capacity hydrogenstorage materials: attributes for automotive applications and techniques for materials discovery Yang, Jun; Sudik, Andrea; Wolverton, Christopher Chem. Soc. Rev., Vol. 39, Issue 2 https://doi.org/10.1039/b802882f	journal	January 2010

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The Simplest Amino-borane H ₂ B=NH ₂ Trapped on a Rhodium Dimer: Pre-Catalysts for Amine-Borane Dehydropolymerization Kumar, Amit; Beattie, Nicholas A.; Pike, Sebastian D. Angewandte Chemie International Edition, Vol. 55, Issue 23 https://doi.org/10.1002/anie.201600898	journal	April 2016
Frustrated Lewis Pair Catalyzed Dehydrogenative Oxidation of Indolines and Other Heterocycles Maier, Alexander F. G.; Tussing, Sebastian; Schneider, Tobias Angewandte Chemie International Edition, Vol. 55, Issue 40 https://doi.org/10.1002/anie.201606426	journal	September 2016
Anionic Chains of Parent Pnictogenylboranes Marquardt, Christian; Kahoun, Tobias; Stauber, Andreas Angewandte Chemie International Edition, Vol. 55, Issue 47 https://doi.org/10.1002/anie.201608875	journal	October 2016
Spontaneous Metal-Free Transfer Hydrogenation of Iminoboranes with Ammonia Borane and Amine Boranes Winner, Lena; Ewing, William C.; Geetharani, K. Angewandte Chemie International Edition, Vol. 57, Issue 38 https://doi.org/10.1002/anie.201807435	journal	August 2018
Metal-Free Dehydrogenation of Amine-Boranes by Tunable N-Heterocyclic Iminoboranes Lui, Melanie W.; Paisley, Nathan R.; McDonald, Robert Chemistry - A European Journal, Vol. 22, Issue 6 https://doi.org/10.1002/chem.201503528	journal	January 2016
Stepwise basis set selection Li, M. W.; Zimmerman, P. M. Journal of Computational Chemistry, Vol. 39, Issue 26 https://doi.org/10.1002/jcc.25363	journal	September 2018
Encapsulating highly catalytically active metal nanoclusters inside porous organic cages Yang, Xinchun; Sun, Jian-Ke; Kitta, Mitsunori Nature Catalysis, Vol. 1, Issue 3 https://doi.org/10.1038/s41929-018-0030-8	journal	March 2018
Supported ammonia borane decomposition through enhanced homopolar B–B coupling Roy, Binayak; Hajari, Animesh; Manna, Joydev Dalton Transactions, Vol. 47, Issue 18 https://doi.org/10.1039/c8dt00789f	journal	January 2018

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