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Sheldon Shore, Small Boranes, and Ammonia
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Abstract
Although trimethylamine [(CH3)3N] and ammonia [H3N] are both recognized as classic Lewis bases, their reactions with the classic Lewis acid borane [BH3 from diborane] was very different. Trimethylamine gave the expected trimethylamine borane [(CH3)3NBH3] while ammonia gave a product called "the diammoniate of diborane." Its structure was shown to be [H2B(NH3)2]+[BH4]- in the late nineteen fifties. The Compound [H2B(NH3)2]+[BH4]- can be viewed as a classic coordination compound in which four-coordinate boron +3 ions are coordinated to the hydride ion and the ammonia molecule as ligands. It is noted that CoCl2 reacts with (CH3)3N and with NH3 in different ways. The "anomaly" is in the bases, not the borane acid.
The paper discusses the early studies on "the diammoniate of diborane" and emphasizes how continuing work done by Sheldon Shore at Ohio State University extended the work on the boranes and answered here-to-fore vexing structural problems on intermediates in the borane and borane-ammonia system. His work made major contributions to synthesis. He worked out techniques to prepare significant quantities of pure [H2B(NH3)2][BH4] and of pure H3NBH3. He also prepared the fascinating, theoretically anticipated compounds K2BH3 and K2B2H6.
The story, as told, shows how a brilliant, imaginative, and thoughtful person, using superb experimental techniques, has been able to develop a difficult experimental system from "black art" to sound science.
Note: This article was prepared from a talk given by the author at a Symposium (8/23/95) honoring Sheldon G. Shore on his sixty-fifth birthday. Dr. Shore is the Charles H. Kimberly Professor of Chemistry at Ohio State University.
Keywords (Audience):
Second-Year UndergraduateKeywords (Domain):
History / PhilosophyKeywords (Subject):
BoronCiting Articles
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This article has been cited by 2 ACS Journal articles (2 most recent appear below).
Theoretical Investigations on the Formation and Dehydrogenation Reaction Pathways of H(NH2BH2)nH (n = 1−4) Oligomers: Importance of Dihydrogen Interactions
Jun Li, Shawn M. Kathmann, Han-Shi Hu, Gregory K. Schenter, Tom Autrey and Maciej GutowskiInorganic Chemistry2010 49 (17), 7710-7720Theoretical Investigations on the Formation and Dehydrogenation Reaction Pathways of H(NH2BH2)nH (n = 1−4) Oligomers: Importance of Dihydrogen Interactions
Jun Li, Shawn M. Kathmann, Han-Shi Hu, Gregory K. Schenter, Tom Autrey and Maciej GutowskiInorganic Chemistry2010 49 (17), 7710-7720The H(NH2BH2)nH oligomers are possible products from dehydrogenation of ammonia borane (NH3BH3) and ammonium borohydride (NH4BH4), which belong to a class of boron−nitrogen−hydrogen (BNHx) compounds that are promising materials for chemical hydrogen ...
The Effects of Chemical Additives on the Induction Phase in Solid-State Thermal Decomposition of Ammonia Borane
David J. Heldebrant, Abhi Karkamkar, Nancy J. Hess, Mark Bowden, Scot Rassat, Feng Zheng, Kenneth Rappe and Tom AutreyChemistry of Materials2008 20 (16), 5332-5336The Effects of Chemical Additives on the Induction Phase in Solid-State Thermal Decomposition of Ammonia Borane
David J. Heldebrant, Abhi Karkamkar, Nancy J. Hess, Mark Bowden, Scot Rassat, Feng Zheng, Kenneth Rappe and Tom AutreyChemistry of Materials2008 20 (16), 5332-5336The induction period for release of hydrogen can be significantly reduced by doping pure samples of AB with DADB or a solid acid such as NH4Cl. The ability to reduce the induction period solves one of the major technical hurdles for considering AB as a ...
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- Received: August 03, 2009
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