Lewis base assisted B–H bond redistribution in borazine and polyborazylene

Davis, Benjamin L.; Rekken, Brian D.; Michalczyk, Ryszard; Garner, Edward B.; Dixon, David A.; Kalviri, Hassan A.; Baker, R. Tom; Thorn, David L.

doi:10.1039/c3cc44748k

Cited by 20 publications

(30 citation statements)

References 23 publications

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“…They indicate the possible presence of BH(NH 2 ) 2 and B(NH 2 ) 3 , respectively. 41 It is evident that release of H 2 occurs simulteneously with NH 3 . Although they are mainly released after melting, a minor amount of these species is released < 100 • C, which coincides with occurence of the cyclo-(NH 2 BH 2 ) 2 .…”

Section: Discussionmentioning

confidence: 95%

High Influence of Potassium Bromide on Thermal Decomposition of Ammonia Borane^†

et al. 2016

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The present work presents a thorough experimental investigation of mechanistic pathways of thermal decomposition of ammonia borane (AB) and its mixture with KBr. A comparative detection and temperature-dependent in-situ monitoring of the decomposition products was done by use of temperature dependent infrared (IR) spectroscopy of both solid (in transmission through KBr pellets and ATR mode) and gaseous products, thermogravimetry (TG) and evolved gas analysis mass spectroscopy (EGA-MS).This enables discrimination of the processes occuring in the bulk from those in the near-surface level. For the first time, a high influence of the KBr matrix on AB decomposition was found and thoroughly investigated. Although KBr does not change the chemical and physical identity of AB at ambient conditions, it dramatically affects its thermal decomposition pathway. It is found that the presence of KBr not only favours the production of diammoniate of diborane in the induction phase, but also enables an efficient catalysis of AB decomposition by NH + 4 ions, present at the KBr − AB interface, which leads to suppression of emission of unwanted gaseous side products other than NH 3 . IR spectroscopy was also used to shed a light on the molecular background of the frequently observed, but never investigated increase of the mass of decomposition products.

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Section: Discussionmentioning

confidence: 95%

High Influence of Potassium Bromide on Thermal Decomposition of Ammonia Borane^†

et al. 2016

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“…18 Typically, the reduction of Fig. 20 Theoretically optimised AB-ammonia dimer in which bonding to both sides of the AB molecule from one ammonia is observed.…”

mentioning

confidence: 99%

Dihydrogen vs. hydrogen bonding in the solvation of ammonia borane by tetrahydrofuran and liquid ammonia

Ingram

Headen

Skipper

et al. 2018

Phys. Chem. Chem. Phys.

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The solvation structures of two systems rich in hydrogen and dihydrogen bonding interactions have been studied in detail experimentally through neutron diffraction with hydrogen/deuterium isotopic substitution. The results were analysed by an atomistic Monte Carlo simulation employing refinement to the experimental scattering data. The systems studied were the hydrogen storage material ammonia borane (NH 3 BH 3 , AB) dissolved in tetrahydrofuran (THF), and liquid ammonia (NH 3 ), the latter in which AB shows unusually high solubility (260 g AB per 100 g NH 3 ) and potential regeneration properties. The full orientational and positional manner in which AB-AB, AB-THF and AB-NH 3 pairs interact with each other were successfully deciphered from the wide Q-range total neutron scattering data. This provided an unprecedented level of detail into such highly (di)hydrogen bonding solute-solvent interactions. In particular this allowed insight into the way in which H-B acts as a hydrogen bond acceptor. The (di)hydrogen bonding was naturally determined to dictate the intermolecular interactions, at times negating the otherwise expected tendency for polar molecules to align themselves with anti-parallel dipole moments. Several causes for the extreme solubility of AB in ammonia were determined, including the ability of ammonia to (di)hydrogen bond to both ends of the AB molecule and the small size of the ammonia molecule relative to AB and THF. The AB B-H to ammonia H dihydrogen bond was found to dominate the intermolecular interactions, occurring almost three times more often than any other hydrogen or dihydrogen bond in the system. The favourability of this interaction was seen on the bulk scale by a large decrease in AB clustering in ammonia compared to in the dihydrogen bond-less THF.

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“…Some of these include ammonia-borane, amine-borane, hydrazine-borane, as well as pyrrolidine-based liquid organic hydrogen carriers [409][410][411][412][413][414][415][416][417][418]. The inverse hydrogenation process of the obtained products has also been explored [419][420][421][422][423]. Several metal catalysts have been investigated for the dehydrocoupling of these hydrogen reservoirs [424][425][426][427][428][429][430][431]; among these, pincer complexes have showed promising features and remarkable activity [432][433][434][435][436][437][438][439][440].…”

Section: Other Hydrogen Storage Systemsmentioning

confidence: 99%

Recent Progress with Pincer Transition Metal Catalysts for Sustainability

2020

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Our planet urgently needs sustainable solutions to alleviate the anthropogenic global warming and climate change. Homogeneous catalysis has the potential to play a fundamental role in this process, providing novel, efficient, and at the same time eco-friendly routes for both chemicals and energy production. In particular, pincer-type ligation shows promising properties in terms of long-term stability and selectivity, as well as allowing for mild reaction conditions and low catalyst loading. Indeed, pincer complexes have been applied to a plethora of sustainable chemical processes, such as hydrogen release, CO2 capture and conversion, N2 fixation, and biomass valorization for the synthesis of high-value chemicals and fuels. In this work, we show the main advances of the last five years in the use of pincer transition metal complexes in key catalytic processes aiming for a more sustainable chemical and energy production.

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Lewis base assisted B–H bond redistribution in borazine and polyborazylene

Cited by 20 publications

References 23 publications

High Influence of Potassium Bromide on Thermal Decomposition of Ammonia Borane^†

High Influence of Potassium Bromide on Thermal Decomposition of Ammonia Borane^†

Dihydrogen vs. hydrogen bonding in the solvation of ammonia borane by tetrahydrofuran and liquid ammonia

Recent Progress with Pincer Transition Metal Catalysts for Sustainability

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Lewis base assisted B–H bond redistribution in borazine and polyborazylene

Cited by 20 publications

References 23 publications

High Influence of Potassium Bromide on Thermal Decomposition of Ammonia Borane†

High Influence of Potassium Bromide on Thermal Decomposition of Ammonia Borane†

Dihydrogen vs. hydrogen bonding in the solvation of ammonia borane by tetrahydrofuran and liquid ammonia

Recent Progress with Pincer Transition Metal Catalysts for Sustainability

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Product

Resources

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High Influence of Potassium Bromide on Thermal Decomposition of Ammonia Borane^†

High Influence of Potassium Bromide on Thermal Decomposition of Ammonia Borane^†