Dehydrogenation of Amine–Boranes Using p‐Block Compounds

Boom, Devin H. A.; Jupp, Andrew R.; Slootweg, J. Chris

doi:10.1002/chem.201900679

Cited by 47 publications

(37 citation statements)

References 136 publications

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“…36 The development of thermally robust and sterically hindered boratriptycene and of FLPs derived from it might thus become feasible. For example, the catalytic dehydrogenation of amine-boranes and the production, 37 storage and transfer of H 2 for hydrogenation reactions can also benefit from bifunctional Lewis acid/base catalysts requiring very low reorganization energies during the dehydrogenation/hydrogenation processes.…”

Section: Further Work and Perspectivesmentioning

confidence: 99%

Non-planar Boron Lewis Acids Taking the Next Step: Development of Tunable Lewis Acids, Lewis Superacids and Bifunctional Catalysts

Chardon

Osi²,

Mahaut³

et al. 2020

Synlett

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Although boron Lewis acids commonly adopt a trigonal planar geometry, a number of compounds in which the trivalent boron atom is located in a pyramidal environment have been described. This review will highlight the recent developments of the chemistry and applications of non-planar boron Lewis acids, including a series of non-planar triarylboranes derived from the triptycene core. A thorough analysis of the properties and of the influence of the pyramidalization of boron Lewis acids on their stereoelectronic properties and reactivities is presented based on recent theoretical and experimental studies.1 Non-planar Trialkylboranes2 Non-planar Alkyl and Aryl-Boronates3 Non-planar Triarylboranes and Alkenylboranes3.1 Previous Investigations on Bora Barrelenes and Triptycenes3.2 Recent Work on Boratriptycenes from Our Research Group4 Applications of Non-planar Boranes4.1 Non-planar Alkyl Boranes and Boronates4.2 Non-planar Triarylboranes (Boratriptycenes)5 Other Non-planar Group 13 Lewis Acids6 Further Work and Perspectives

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Section: Further Work and Perspectivesmentioning

confidence: 99%

Non-planar Boron Lewis Acids Taking the Next Step: Development of Tunable Lewis Acids, Lewis Superacids and Bifunctional Catalysts

Chardon

Osi²,

Mahaut³

et al. 2020

Synlett

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“…Since catalytic routes can overcome these shortcomings, various homogeneous and heterogeneous catalysts for dehydrogenation/dehydrocoupling of amine boranes have been reported, most of which are based on d‐block elements, many on precious metals, such as rhodium or iridium . Although these operate at room temperature and with low catalyst loadings, main group element and in particular s‐block metal‐based catalysts have been investigated in view of lower element costs and ready availability . With respect to magnesium, for example, Hill and co‐workers reported the use of dialkyl‐ and 1,3‐diketimine magnesium compounds in the dehydrocoupling of dimethylamine borane (Figure ; I – III ) .…”

Section: Introductionmentioning

confidence: 99%

Magnesocenophane‐Catalyzed Amine Borane Dehydrocoupling

Wirtz

Haider

Hüch

et al. 2020

Chemistry A European J

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The Lewis acidities of as eries of [n]magnesocenophanes (1a-d)h ave been investigatedc omputationally and found to be af unctiono ft he tilt of the cyclopentadienyl moieties. Their catalytic abilities in amine borane dehydrogenation/dehydrocoupling reactions have been probed, and C[1]magnesocenophane (1a)h as been shown to effectively catalyze the dehydrogenation/dehydrocoupling of dimethyl-amine borane (2a)a nd diisopropylamine borane (2b)u nder ambient conditions. Furthermore, the mechanism of the reaction with 2a has been investigated experimentally and computationally,a nd the results imply al igand-assisted mechanism involving stepwise protona nd hydride transfer, with dimethylaminoborane as the key intermediate. [a] E = bridginga tom(s) of ansa bridge;[ b] n = number of bridging atom(s) in ansa bridge.Scheme6.Reactionofm agnesium complex 5 with 2,2-dicyclopentadienylpropanetog ive magnesocenophane 1a.Scheme8.Simplified proposed catalytic cycle (coordinating solventm olecules omitted) for the dehydrogenation of Me 2 NH·BH 3 (2a)and Me 2 NHÀBH 2 ÀNMe 2 À BH 3 (3b)t oc yclic diborazane 3a,catalyzedbym agnesocenophane 1a.Scheme7.Dehydrocoupling of Me 2 NHÀBH 2 ÀNMe 2 ÀBH 3 (3b)catalyzed by 1a. Figure 10. Calculated reaction pathwaysfor the dehydrogenation of dimethylamine borane (2a)v ia dimethylaminoborane (4a), catalyzed by 1a·dme (calculated at the B3LYP-D3/def2-TZVP leveloft heory [11] ;hydrogena toms of CH 2 and CH 3 groupso mittedf or clarity).

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“…Interest in dehydrocoupling reactions has recently risen, as it provides a clean and atom-efficient route to new element-element bonds, with the concomitant formation of dihydrogen, which has numerous applications in organic synthesis and materials chemistry [17][18][19]. The formation of dihydrogen in these types of reactions has gained the most attention due to the potential for hydrogen storage and therefore sustainable energy sources.…”

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confidence: 99%

NHI- and NHC-Supported Al(III) Hydrides for Amine–Borane Dehydrocoupling Catalysis

et al. 2019

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The catalytic dehydrocoupling of amine-boranes has recently received a great deal of attention due to its potential in hydrogen storage applications. The use of aluminum catalysts for this transformation would provide an additional cost-effective and sustainable approach towards the hydrogen economy. Herein, we report the use of both N-heterocyclic imine (NHI)-and carbene (NHC)-supported Al(III) hydrides and their role in the catalytic dehydrocoupling of Me 2 NHBH 3 . Differences in the σ-donating ability of the ligand class resulted in a more stable catalyst for NHI-Al(III) hydrides, whereas a deactivation pathway was found in the case of NHC-Al(III) hydrides.

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Dehydrogenation of Amine–Boranes Using p‐Block Compounds

Cited by 47 publications

References 136 publications

Non-planar Boron Lewis Acids Taking the Next Step: Development of Tunable Lewis Acids, Lewis Superacids and Bifunctional Catalysts

Non-planar Boron Lewis Acids Taking the Next Step: Development of Tunable Lewis Acids, Lewis Superacids and Bifunctional Catalysts

Magnesocenophane‐Catalyzed Amine Borane Dehydrocoupling

NHI- and NHC-Supported Al(III) Hydrides for Amine–Borane Dehydrocoupling Catalysis

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