Brønsted and Lewis Base Behavior of Sodium Amidotrihydridoborate (NaNH<sub>2</sub>BH<sub>3</sub>)

Chen, Ximeng; Li, Huizhen; Yang, Qiuyu; Wang, Ruirui; Hamilton, Ewan J. M.; Zhang, Jie; Chen, Xuenian

doi:10.1002/ejic.201700556

Cited by 21 publications

(17 citation statements)

References 56 publications

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“…Complex mixture A, Complex mixture B, Mixture C, Complex mixture D.The diffraction patterns of sodium imidazolate and cobalt metaphosphate are in good agreement with published literature of Chen et al21 and Ahn et al,22 respectively. The complex mixture D consists of cobalt metaphosphate, Co(PO 3 ) 2 , sodium imidazolate, C 3 H 3 N 2 Na, cobalt sulfate hexahydrate, [Co(H 2 O) 6 ]SO 4 , and imidazole, C 3 H 4 N 2 .…”

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confidence: 89%

Heat repellent behavior of cobalt‐based imidazole containing phosphate and meta‐phosphate complex mixtures

2021

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Four different mixtures such as complex mixture A, [Co(H 2 O) 4 (HPO 4 )] (C 3 H 4 N 2 )(H 2 O) 2 Á 0.2 (C 3 H 4 N 2 ), complex mixture B, [Co(H 2 O) 6 ](H 2 PO 4 )(OH) (H 2 O) Á(C 3 H 4 N 2 ) 2 , mixture C, 0.34 Co(PO 3 ) 2 Á0.15(C 3 H 3 N 2 Na), and complex mixture D, 0.03Co(PO 3 ) 2 Á0.25(C 3 H 3 N 2 Na) Á0.1 [Co(H 2 O) 6 ]SO 4 .H 2 OÁ0.6 (C 3 H 4 N 2 ), were synthesized using ortho-phosphoric acid and meta-phosphoric acid with cobalt sulfate heptahydrate and imidazole in ambient conditions. These mixtures have been well characterized by different thermo-analytical techniques. Differential Scanning Calorimetry (DSC) has been carried out at different heating rates such as 5, 10, 20, and 30 K min −1 at atmospheric conditions. The specific heat capacity was measured at low temperatures up to 173 K for mixture C at a rate of 10 K min −1 . From the thermal analysis, it can be observed that the complex mixtures A and B prepared using phosphoric acid and mixture C prepared using meta-phosphoric acid behave as heat repellent material owing to their exothermic behavior at high temperature. The anomalous negative specific heat capacity exhibited by the mixtures is explained using partial molar quantities. Among all the four complex mixtures, the complex mixture A has been found to be the best heat repellent material.The complex mixture B can be used as heat storage material up to temperature $550 K due to its endothermic behavior. These phosphate materials can be used for longer period of time due to their stability and insolubility in aqueous media. The heat can be extracted from any system that is coated with these phosphate mixtures using high conductivity copper rod. K E Y W O R D SDSC, heat repellent material, negative heat capacity, partial molar quantities | INTRODUCTIONConsumption of energy has increased exponentially over the years in all aspects of human life. Because of this, the modern technological man is striving hard to explore all possible options to cater to the ever-increasing demand for energy. Conventional energy reserves, viz. coal and fossil fuels, have already been exploited to their maximum extent and their collateral impacts of environmental pollution and global warming leading to climate change. It is indeed essential to scout around various viable sources of renewable energy, such as extracting

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confidence: 89%

Heat repellent behavior of cobalt‐based imidazole containing phosphate and meta‐phosphate complex mixtures

2021

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“…Thus it is somewhat unsurprising that little research effort has been invested into understanding this reaction . Generally, there are four fates of the newly formed B−H−B unit (Figure , i – iv ): ( i ) the bridging hydrogen bond is cleaved and the hydride transfers from one boron atom to the other;, This constitutes a hydride transfer, a type of reaction that will not be discussed at length herein; ( ii ) the newly formed B−H−B bond reversibly reverts back to the starting materials; ( iii ) the formed B−H−B bond is maintained in the final product in the presence of a suitable environment; and ( iv ) the formed B−H−B bond is stabilized by the subsequent formation of a new chemical bond to give a cyclic molecule ,…”

Section: The Nucleophilicity Of the B−h Bonding Pair Electronsmentioning

confidence: 99%

“…Based on this renewed interest, the basic chemistry of these species has been developed further. A recent investigation indicated that the reaction of NaNH 2 BH 3 with NH 3 ⋅BH 3 or THF⋅BH 3 produces different products (Scheme ) ,. When NaNH 2 BH 3 was reacted with NH 3 ⋅BH 3 in THF under reflux, Na[NH 2 (BH 3 ) 2 ] was formed as the major product, with polyaminoborane [NH 2 BH 2 ] n , and NaBH 4 as minor products (Scheme A).…”

Section: The Nucleophilicity Of the B−h Bonding Pair Electronsmentioning

confidence: 99%

A New Perspective on Borane Chemistry: The Nucleophilicity of the B−H Bonding Pair Electrons

et al. 2019

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A number of recently discovered nucleophilic boron compounds, such as boryl anions and borylenes, are breaking the rules regarding boron and boron‐containing compounds and their reputation as Lewis acids/electrophiles. In a similar fashion, the B−H bonding pair electrons in boranes also show nucleophilicity which is ascribed to the lower electronegativity of boron relative to that of hydrogen. However, this nucleophilicity of the B−H bond has received far less attention. Explorations of the nucleophilicity of the B−H bonding pair electrons have led to the formation of B−H−B bonded units and B−H⋅⋅⋅H−Y dihydrogen bonds, based on which new chemistry has been uncovered, including the elucidation of the mechanism of formation of aminodiborane (ADB), the diammoniate of diborane (DADB), and lithium or sodium salts of octahydrotriborates (B3H8−), as well as the development of more convenient and straightforward synthetic routes to these reagents. Moreover, the recognition of the nucleophilic properties of the B−H bonding pair electrons will also help to more deeply understand the different mechanisms operating in hydroboration reactions.

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“…Boron compounds are of interest because of their unique properties as Lewis acids [1][2][3][4], hydrogen storage compounds [5][6][7][8], and as catalysts in chemical reactions [9,10]. Also, because of the electron deficiency of the B atom, boron compounds are used as strong anion receptors [11,12].…”

Section: Introductionmentioning

confidence: 99%

Clustering of H2SO4 with BX3 (X = H, F, Cl, Br, CN, OH) compounds creates strong acids and superacids

Valadbeigi

Kurtén

2019

Computational and Theoretical Chemistry

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The interaction of H2SO4 with boron compounds including BH3, BF3, BCl3, BBr3, B(CN)3 and B(OH)3 was studied computationally using the B97xD density functional. All the BX3 compounds except B(OH)3 bind to H2SO4 via both SOH...X hydrogen bonds, and interactions between the B atoms and the S=O oxygen atoms. B(OH)3 interacts with H2SO4 solely through hydrogen bonds. B(CN)3 and BCl3 exhibit the strongest and weakest interactions with H2SO4, respectively. Natural bond orbital (NBO) analysis shows that the relative weakness of the H2SO4-BCl3 interaction may be due to π-bonding between the B and Cl atoms, and the occupation of the pz orbital of the B atom. The strong electron withdrawing groups CN in B(CN)3 intensify electron deficiency of B atom and promote its tendency to capture electrons of oxygen atom of O=S group. Atoms in molecules (AIM) calculations show bond critical points (BCP) between the X groups of BX3 and the hydrogen atoms of H2SO4 for all cases except X = OH. Enthalpies and Gibbs free energies of deprotonation in the gas phase (∆Hacid, ∆Gacid) were calculated for (BX3)H2SO4 and (BX3)2H2SO4 complexes. These data revealed that clustering of BX3 with H2SO4 enhances the acidity of H2SO4 by about 9-58 kcal.mol-1. The (B(CN)3)2H2SO4 cluster had ∆Hacid and ∆Gacid values of 255.0 and 246.7 kcal.mol-1 , respectively, and is the strongest Brønsted acids among the (BX3)2H2SO4 clusters.

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Brønsted and Lewis Base Behavior of Sodium Amidotrihydridoborate (NaNH₂BH₃)

Cited by 21 publications

References 56 publications

Heat repellent behavior of cobalt‐based imidazole containing phosphate and meta‐phosphate complex mixtures

Heat repellent behavior of cobalt‐based imidazole containing phosphate and meta‐phosphate complex mixtures

A New Perspective on Borane Chemistry: The Nucleophilicity of the B−H Bonding Pair Electrons

Clustering of H2SO4 with BX3 (X = H, F, Cl, Br, CN, OH) compounds creates strong acids and superacids

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Brønsted and Lewis Base Behavior of Sodium Amidotrihydridoborate (NaNH2BH3)

Cited by 21 publications

References 56 publications

Heat repellent behavior of cobalt‐based imidazole containing phosphate and meta‐phosphate complex mixtures

Heat repellent behavior of cobalt‐based imidazole containing phosphate and meta‐phosphate complex mixtures

A New Perspective on Borane Chemistry: The Nucleophilicity of the B−H Bonding Pair Electrons

Clustering of H2SO4 with BX3 (X = H, F, Cl, Br, CN, OH) compounds creates strong acids and superacids

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Brønsted and Lewis Base Behavior of Sodium Amidotrihydridoborate (NaNH₂BH₃)

Clustering of H2SO4 with BX3 (X = H, F, Cl, Br, CN, OH) compounds creates strong acids and superacids