Reactive insights into the selective dehydrogenation of ethylene diamine bisborane facilitated by phosphonium based Ionic Liquids

Kundu, Debashis; Banerjee, Basudhrity; Pugazhenthi, G.; Banerjee, Tamal

doi:10.1016/j.ijhydene.2016.09.215

Cited by 17 publications

(15 citation statements)

References 45 publications

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“…The catalytic role of phosphonium based ILs was investigated in the thermal dehydrogenation of ethylene diamine bisborane (EDAB) ( 103 ) that was performed at high vacuum (4x10 −2 mbar) and at 95 °C and 105 °C, respectively . The chosen ILs were trihexyl (tetradecyl) phosphonium bis (2,4,4‐trimethylphenyl) phosphinate (TDTHPPhosph) and trihexyl(tetradecyl)‐phosphonium dicyanamide (TDTHPDCA) because they are thermally stable, do not degrade during dehydrogenation and also presents basic environment due to the absence of acidic hydrogen.…”

Section: The Use Of Phosphonium Ionic Liquids As Catalystsmentioning

confidence: 99%

Phosphonium‐Based Ionic Liquids Used as Reagents or Catalysts

2019

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The role and enlarged importance of ionic liquids (ILs) in chemical reactions were already exhaustively demonstrated. The aim of this review is to promote the family of the phosphonium‐based ILs used as reagents and catalysts, which gained increased interest in the last decade. The common and beneficial properties of ILs refer to their negligible vapour pressure, non‐toxicity, reusability, and high thermal stability. Therefore, phosphonium‐based ionic liquids are used successfully as catalysts and reagents in many chemical reactions, and additionally allow the syntheses in mild reaction conditions. Phosphonium ILs have proved their catalytic efficiency in many reactions such as epoxidation of olefins and allylic alcohol, in synthesis of alpha‐aminophosphonates, beta‐ketophosphonates, nitrogen‐containing bisphosphonates, the Michaelis‐Arbuzov reactions, esterification, coupling reaction, aromatic chlorination, dehydrogenation. The major advantage of phosphonium‐based ILs used as catalysts is that they can be reused with only little loss of catalytic activity. Phosphonium ILs revealed their potential as Wittig reagents, halogenation reagents for bromination and bromo‐chlorination reactions with alkenes and alkynes, as monomer and as initiator in frontal polymerization of acrylates. From the literature data, it can be concluded that due to their structure and physical‐chemical properties phosphonium ILs can be tailored function of their purpose.

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Section: The Use Of Phosphonium Ionic Liquids As Catalystsmentioning

confidence: 99%

Phosphonium‐Based Ionic Liquids Used as Reagents or Catalysts

2019

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“…Traditional belief is unlike the dehydrogenation of AB, dehydrogenation of pure EDAB, and EDAB/IL systems do not produce any induction period . However, 1‐butyl‐3‐methylimidazolium methylsulfonate [BMIM][OMs] is reported to facilitate thermolysis with an induction period of 30 min in dehydrogenation .…”

Section: Resultsmentioning

confidence: 99%

“…In a subsequent report, Banerjee et al employed reactive force field simulation to elucidate the EDAB/IL desorption mechanism. Kundu et al carried out mechanistic investigation of hydrogen release from EDAB/phosphonium IL system. The phosphonium ILs facilitated the selective formation of higher repeating unit containing EDAB oligomer, compared with the acetate‐based systems.…”

Section: Resultsmentioning

confidence: 99%

“…The potential role of ILs as solvent and catalysis can thus be tuned for dehydrogenation of amine boranes. The first reported work of IL‐facilitated dehydrogenation of AB was carried out by Bluhm et al, and the mechanistic investigation was given by Himmelberger et al Dehydrogenation of EDAB and other carbon derivatives of amine boranes using IL has been reported in quite a few of scientific reports . However, most of these works preferred to exploit the amine boranes in imidazolium cation containing ILs, which are acidic in nature.…”

Section: Introductionmentioning

confidence: 99%

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Effect of thiocyanate‐based ionic liquids on the dehydrogenation of amine boranes: Experimental and molecular modeling studies

Kundu

Chakma

Pugazhenthi

et al. 2019

Asia-Pacific J Chem Eng

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The present investigation reports the effect of thiocyanate-based ionic liquid (IL) on the thermal dehydrogenation of amine boranes. Fifteen ILs based on thiocyanate anion comprising cations from imidazolium, pyrrolidinium, and ammonium family were screened by a priori prediction of infinite dilution activity coefficient using the quantum chemical-based conductor-like screening model segment activity coefficient method. The IL with the highest predicted solubility of amine boranes converged to 1-ethyl-3-methylimidazolium thiocyanate ([EMIM] [SCN]) that was then used for the dehydrogenation reaction. In the IL medium, ammonia borane (AB) and ethylene diamine bisborane (EDAB) were found to produce~1.64 equivalent of hydrogen with an induction period of 60 min and~2.37 equivalent of hydrogen having an induction period of 30 min, respectively. It was observed that the mixture of AB and EDAB in [EMIM][SCN] produced prolonged induction period of 210 min. After 240 min, the mixed amine boranes only produce 0.43 equivalent of H 2 . To elucidate this slow dynamics, Density Functional Theory (DFT) optimized geometries followed by the natural bond orbital analysis revealed the formation of hydrogen bond between IL and amine borane moiety. Further, the presence of the stronger dihydrogen bond among the protic and hydridic hydrogens was also observed in AB + EDAB/[EMIM][SCN] system, resulting in longer induction period for dehydrogenation. KEYWORDS amine borane, boron NMR, natural bond orbital, thiocyanate ionic liquid

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“…Our previous investigation with phosphonium IL-facilitated dehydrogenation of EDAB suggests that the intermediate radicals are more stable in the basic environment of phosphonium ILs, despite lower yield of H 2 , than in imidazolium-based ILs. 18 Because of the lower density than water, the phosphonium-based ILs are particularly useful for separation of biobutanol, 19 rare earth, and noble metals 20 from aqueous streams. Further, they are suitable for the application of super capacitors because of an enhanced electrochemical window.…”

Section: Introductionmentioning

confidence: 99%

Ionic Liquid Facilitated Dehydrogenation of tert-Butylamine Borane

et al. 2018

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The current work reports ionic liquid (IL) facilitated dehydrogenation of tert -butylamine borane (TBAB) at 90 and 105 °C. For the screening of potential IL solvent, solubility predictions of TBAB in ILs were performed by the conductor-like screening model segment activity coefficient (COSMO-SAC) model. The COSMO-SAC model predicted a logarithmic infinite dilution activity coefficient of −6.66 and −7.31 for TBAB in 1-butyl-3-methylimidazolium acetate [BMIM][OAc] and trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate [TDTHP][Phosph], respectively. Hydrogen (1.95 equiv) was seen to release from TBAB/[BMIM][OAc] at 105 °C, whereas TBAB/[TDTHP][Phosph] produced 1.63 equiv of hydrogen after 360 min of dehydrogenation. The proton nuclear magnetic resonance ( 1 H NMR) characterization of TBAB/IL systems revealed the structural integrity of ILs during dehydrogenation. Further characterization through the boron NMR ( 11 B NMR) technique disclosed the time-resolved formation and stability of the starting compound, intermediate boron moieties, and product distribution. The 11 B NMR characterization also revealed the fact that the TBAB/[TDTHP][Phosph] mixture dehydrogenates via bimolecular addition of TBAB by forming borohydride anion (−BH 4 – ). It was seen to oligomerize with the subsequent addition of TBAB in the oligomer chain. For the TBAB/[BMIM][OAc] system, the 11 B NMR characterization could not identify the borohydride anion but confirmed a faster formation of the B=N moiety when compared to the TBAB/[TDTHP][Phosph] system. On the basis of the NMR characterization, IL-facilitated dehydrogenation mechanism of TBAB is proposed.

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Reactive insights into the selective dehydrogenation of ethylene diamine bisborane facilitated by phosphonium based Ionic Liquids

Cited by 17 publications

References 45 publications

Phosphonium‐Based Ionic Liquids Used as Reagents or Catalysts

Phosphonium‐Based Ionic Liquids Used as Reagents or Catalysts

Effect of thiocyanate‐based ionic liquids on the dehydrogenation of amine boranes: Experimental and molecular modeling studies

Ionic Liquid Facilitated Dehydrogenation of tert-Butylamine Borane

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