Cobalt-catalyzed ammonia borane dehydrocoupling and transfer hydrogenation under aerobic conditions

Pagano, Justin K.; Stelmach, John P. W.; Waterman, Rory

doi:10.1039/c5dt00108k

Cited by 51 publications

(49 citation statements)

References 34 publications

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“…Various dehydrogenation and transfer hydrogenation protocols have been developed with precious metal catalysts, and the underlying mechanisms have been thoroughly studied . By contrast, dehydrogenations are far less advanced with the abundant and cheaper late 3d metals, despite the recent progress with Ti, Mn, Fe, Co, and Ni catalysts …”

Section: Introductionmentioning

confidence: 99%

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Amine‐Borane Dehydrogenation and Transfer Hydrogenation Catalyzed by α‐Diimine Cobaltates

Maier

Sandl

Shenderovich

et al. 2018

Chemistry A European J

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Anionic α‐diimine cobalt complexes, such as [K(thf)1.5{(DippBIAN)Co(η4‐cod)}] (1; Dipp=2,6‐diisopropylphenyl, cod=1,5‐cyclooctadiene), catalyze the dehydrogenation of several amine‐boranes. Based on the excellent catalytic properties, an especially effective transfer hydrogenation protocol for challenging olefins, imines, and N‐heteroarenes was developed. NH3BH3 was used as a dihydrogen surrogate, which transferred up to two equivalents of H2 per NH3BH3. Detailed spectroscopic and mechanistic studies are presented, which document the rate determination by acidic protons in the amine‐borane.

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Section: Introductionmentioning

confidence: 99%

“…Although a number of iron catalysts for amine‐borane dehydrogenations have been studied recently, effective cobalt catalysts are scarce . To the best of our knowledge, only three well‐defined molecular cobalt catalysts have been reported to date.…”

Section: Introductionmentioning

confidence: 99%

Amine‐Borane Dehydrogenation and Transfer Hydrogenation Catalyzed by α‐Diimine Cobaltates

Maier

Sandl

Shenderovich

et al. 2018

Chemistry A European J

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“…Ammonia-borane is a promising chemical hydrogen storage material due to its high hydrogen content 1 and the fact that a variety of transition metal compounds have the ability of promoting its kinetically controlled dehydrogenation, including complexes of Fe, 2 Ru, 3 Os, 4 Co, 5 Rh, 6 Ir, 7 Ni, 8 and Pd. Inner-and outer-sphere mechanisms have been generally considered in order to rationalize the dehydrogenation (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Ammonia Borane Dehydrogenation Promoted by a Pincer-Square-Planar Rhodium(I) Monohydride: A Stepwise Hydrogen Transfer from the Substrate to the Catalyst

Esteruelas

Nolis²,

Oliván

et al. 2016

Inorg. Chem.

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ABSTRACT:The , and the tandem ammonia-borane dehydrogenation -cyclohexene hydrogenation. DFT calculations on the ammonia-borane dehydrogenation suggest that the process takes place by means of cis-κ 2 -PP-species, through four stages including: i) Shimoi type coordination of ammonia-borane, ii) homolytic addition of the coordinated H-B bond to afford a five-coordinate-dihydride-boryl-rhodium(III) intermediate, iii) reductive-intramolecular proton transfer from the NH 3 group to one of the hydride ligands, and iv) release of H 2 from the resulting square-planar hydridedihydrogen-rhodium(I) intermediate.

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“…Recently, various nanoparticles have been synthesized and applied as catalysts for the dehydrogenation of AB . There are very few reports available on the utilization of AB for transfer hydrogenation reactions of organic compounds, hence, there is a need to explore more active catalytic systems for tandem dehydrogenation and transfer hydrogenation reactions. The N ‐formamides are a very important class of organic compounds, which are extensively used in the field of organic synthesis.…”

Section: Resultsmentioning

confidence: 99%

Ru@PsIL‐Catalyzed Synthesis of N‐Formamides and Benzimidazole by using Carbon Dioxide and Dimethylamine Borane

2018

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This work reports the synthesis and characterization of ruthenium nanoparticles (Ru NPs) supported on polymeric ionic liquids (PILs). This catalyst shows high catalytic activity towards the N‐formylation of amines and synthesis of benzimidazoles from 1,2‐diamines and carbon dioxide (CO2) by reductive dehydrogenation of dimethylamine borane. This methodology shows excellent functional group tolerance with broad substrate scope towards the synthesis of N‐formamides and benzimidazoles. Interestingly, this protocol also provides the tandem reduction of 2‐nitroamines and CO2 to synthesize benzimidazoles. It was proposed that the ionic liquid phase of the polymer plays pivotal roles such as assisting the stabilization of nanoparticles electrostatically, providing an ionic environment, and controlling the easy access of the substrates/reagents to the active sites. The developed methodology utilizes CO2 as a C1 source and water/ethanol as a green solvent system. Additionally, the catalyst was found to be recyclable in nature and shows five consecutive recycling runs without significant loss in its activity.

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Cobalt-catalyzed ammonia borane dehydrocoupling and transfer hydrogenation under aerobic conditions

Cited by 51 publications

References 34 publications

Amine‐Borane Dehydrogenation and Transfer Hydrogenation Catalyzed by α‐Diimine Cobaltates

Amine‐Borane Dehydrogenation and Transfer Hydrogenation Catalyzed by α‐Diimine Cobaltates

Ammonia Borane Dehydrogenation Promoted by a Pincer-Square-Planar Rhodium(I) Monohydride: A Stepwise Hydrogen Transfer from the Substrate to the Catalyst

Ru@PsIL‐Catalyzed Synthesis of N‐Formamides and Benzimidazole by using Carbon Dioxide and Dimethylamine Borane

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