The Reaction of Hydrogen Halides with Tetrahydroborate Anion and Hexahydro-closo-hexaborate Dianion

Golub, Igor E.; Filippov, Oleg A.; Belkova, Natalia V.; Epstein, Lina M.; Shubina, Elena S.

doi:10.3390/molecules26123754

Cited by 10 publications

(7 citation statements)

References 88 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In par-ticular, all solvents have been explicitly accounted for. Our results are in good agreement with those obtained for hydrogen atom substitution for chlorine [28,29].…”

Section: Resultssupporting

confidence: 91%

“…Proton migration led to the formation of an intermediate in which the dihydrogen H 2 fragment coordinated to one boron atom of the cluster cage. The nature of the interaction between the boron atom and the H 2 fragment has been discussed in detail in several articles [28,29]. As in the case of transition state structures, the anion [B 10 H 7 O 2 CCH 3 (H 2 )] − has three possible isomers: H 2 _B 1 , H 2 _B 3 and H 2 _B 4 (Figure 3).…”

Section: Resultsmentioning

confidence: 99%

“…Brønsted and Lewis acids can act as an electrophile inducer [26,27]. For closo-decaborate anions, the most common inducers are CF 3 COOH and CF 3 SO 3 H. The mechanism of the EINS process has been described in detail in several articles [28][29][30]. This process involves several steps.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Theoretical Insight on the Formation Mechanism of a Trisubstituted Derivative of Closo-Decaborate Anion [B10H7O2CCH3(NCCH3)]0

et al. 2023

View full text Add to dashboard Cite

A theoretical modelling of the interaction process between a protonated complex of carboxonium derivative [2,6-B10H8O2CCH3*Hfac]0 and acetonitrile molecule CH3CN was carried out. As a result of the process, a trisubstituted [B10H7O2CCH3(NCCH3)]0 derivative was formed. This reaction has an electrophile-induced nucleophilic substitution (EINS) mechanism. The main intermediates and transition states of the substitution process were established. As in the case of all previously investigated EINS processes, the key intermediate was an anion with a dihydrogen H2 fragment attached to one boron atom (B(H2) structure motif). The process of nucleophilic substitution can proceed on a different position of the cluster cage. The main potential pathways were assessed. It was established that substitution on the B4 position of the cluster cage was the most energetically favourable, and the [2,4,6-B10H7O2CCH3(NCCH3)]0 isomer was formed.

show abstract

“…In par-ticular, all solvents have been explicitly accounted for. Our results are in good agreement with those obtained for hydrogen atom substitution for chlorine [28,29].…”

Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Theoretical Insight on the Formation Mechanism of a Trisubstituted Derivative of Closo-Decaborate Anion [B10H7O2CCH3(NCCH3)]0

et al. 2023

View full text Add to dashboard Cite

show abstract

“…However, despite the widespread occurrence of EINS process in laboratory practice, its mechanism has been studied in only a few papers. The mechanism of chlorination of closo -borates with the HCl molecule has been investigated in several publications [ 54 , 55 ]. This paper reports on comprehensive investigations of the key stages of the EINS process.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Disubstituted Carboxonium Derivatives of Closo-Decaborate Anion [2,6-B10H8O2CC6H5]−: Theoretical and Experimental Study

et al. 2023

View full text Add to dashboard Cite

A comprehensive study focused on the preparation of disubstituted carboxonium derivatives of closo-decaborate anion [2,6-B10H8O2CC6H5]− was carried out. The proposed synthesis of the target product was based on the interaction between the anion [B10H11]− and benzoic acid C6H5COOH. It was shown that the formation of this product proceeds stepwise through the formation of a mono-substituted product [B10H9OC(OH)C6H5]−. In addition, an alternative one-step approach for obtaining the target derivative is postulated. The structure of tetrabutylammonium salts of carboxonium derivative ((C4H9)4N)[2,6-B10H8O2CC6H5] was established with the help of X-ray structure analysis. The reaction pathway for the formation of [2,6-B10H8O2CC6H5]− was investigated with the help of density functional theory (DFT) calculations. This process has an electrophile induced nucleophilic substitution (EINS) mechanism, and intermediate anionic species play a key role. Such intermediates have a structure in which one boron atom coordinates two hydrogen atoms. The regioselectivity for the process of formation for the 2,6-isomer was also proved by theoretical calculations. Generally, in the experimental part, the simple and available approach for producing disubstituted carboxonium derivative was introduced, and the mechanism of this process was investigated with the help of theoretical calculations. The proposed approach can be applicable for the preparation of a wide range of disubstituted derivatives of closo-borate anions.

show abstract

“…B 12 H 12 2− is particularly stable and can thus also act as a detrimental thermodynamic sink for further dehydrogenation reactions. The properties of closo-hydroborates and related anions were addressed in several recent publications [6,[25][26][27][28]. New research on the thermal properties of closo-hydroborate salts revealed a high-temperature phase transition in Na 2 B 12 H 12 leading to a superionic phase [29].…”

Section: Introductionmentioning

confidence: 99%

Boron Hydrogen Compounds: Hydrogen Storage and Battery Applications

Hagemann

2021

Molecules

View full text Add to dashboard Cite

About 25 years ago, Bogdanovic and Schwickardi (B. Bogdanovic, M. Schwickardi: J. Alloys Compd. 1–9, 253 (1997) discovered the catalyzed release of hydrogen from NaAlH4. This discovery stimulated a vast research effort on light hydrides as hydrogen storage materials, in particular boron hydrogen compounds. Mg(BH4)2, with a hydrogen content of 14.9 wt %, has been extensively studied, and recent results shed new light on intermediate species formed during dehydrogenation. The chemistry of B3H8−, which is an important intermediate between BH4− and B12H122−, is presented in detail. The discovery of high ionic conductivity in the high-temperature phases of LiBH4 and Na2B12H12 opened a new research direction. The high chemical and electrochemical stability of closo-hydroborates has stimulated new research for their applications in batteries. Very recently, an all-solid-state 4 V Na battery prototype using a Na4(CB11H12)2(B12H12) solid electrolyte has been demonstrated. In this review, we present the current knowledge of possible reaction pathways involved in the successive hydrogen release reactions from BH4− to B12H122−, and a discussion of relevant necessary properties for high-ionic-conduction materials.

show abstract

The Reaction of Hydrogen Halides with Tetrahydroborate Anion and Hexahydro-closo-hexaborate Dianion

Cited by 10 publications

References 88 publications

Theoretical Insight on the Formation Mechanism of a Trisubstituted Derivative of Closo-Decaborate Anion [B10H7O2CCH3(NCCH3)]0

Theoretical Insight on the Formation Mechanism of a Trisubstituted Derivative of Closo-Decaborate Anion [B10H7O2CCH3(NCCH3)]0

Synthesis of Disubstituted Carboxonium Derivatives of Closo-Decaborate Anion [2,6-B10H8O2CC6H5]−: Theoretical and Experimental Study

Boron Hydrogen Compounds: Hydrogen Storage and Battery Applications

Contact Info

Product

Resources

About