Exploring the mechanisms of aqueous methanol dehydrogenation catalyzed by defined PNP Mn and Re pincer complexes under base-free as well as strong base conditions

Wei, Zhihong; Aguirre, Adiran de; Junge, Kathrin; Beller, Matthias; Jiao, Haijun

doi:10.1039/c8cy00746b

Cited by 36 publications

(18 citation statements)

References 71 publications

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“…Apart from the O‐coordination, we located the complex of C−H coordination 3 A2 , which is responsible for the activation and dissociation of the C−H bond, and higher in energy than 3 A1 by 25.28 kcal mol −1 . In 3 A2 , the H−C distance is 1.235 Å, the Co−H distance is 1.805 Å and the H‐to‐O H‐bonding distance is 1.822 Å.…”

Section: Figurementioning

confidence: 99%

Cobalt‐Catalyzed Aqueous Dehydrogenation of Formic Acid

Zhou

Wei

Spannenberg

et al. 2019

Chemistry A European J

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Among the known liquid organic hydrogen carriers, formic acid attracts increasing interest in the context of safe and reversible storage of hydrogen. Here, the first molecularly defined cobalt pincer complex is disclosed for the dehydrogenation of formic acid in aqueous medium under mild conditions. Crucial for catalytic activity is the use of the specific complex 3 . Compared to related ruthenium and manganese complexes 7 and 8 , this optimal cobalt complex showed improved performance. DFT computations support an innocent non‐classical bifunctional outer‐sphere mechanism on the triplet state potential energy surface.

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Section: Figurementioning

confidence: 99%

Cobalt‐Catalyzed Aqueous Dehydrogenation of Formic Acid

Zhou

Wei

Spannenberg

et al. 2019

Chemistry A European J

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“…The same group carried out mechanistic studies on aqueous methanol dehydrogenation using well-defined manganese and rhenium catalysts, under both base-free as well as strongly basic conditions [341]. Fu used DFT calculations to propose a self-catalytic role of methanol in ruthenium PNP-catalyzed dehydrogenation [342].…”

Section: Methanol Dehydrogenationmentioning

confidence: 99%

Recent Progress with Pincer Transition Metal Catalysts for Sustainability

2020

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Our planet urgently needs sustainable solutions to alleviate the anthropogenic global warming and climate change. Homogeneous catalysis has the potential to play a fundamental role in this process, providing novel, efficient, and at the same time eco-friendly routes for both chemicals and energy production. In particular, pincer-type ligation shows promising properties in terms of long-term stability and selectivity, as well as allowing for mild reaction conditions and low catalyst loading. Indeed, pincer complexes have been applied to a plethora of sustainable chemical processes, such as hydrogen release, CO2 capture and conversion, N2 fixation, and biomass valorization for the synthesis of high-value chemicals and fuels. In this work, we show the main advances of the last five years in the use of pincer transition metal complexes in key catalytic processes aiming for a more sustainable chemical and energy production.

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“…The choice of methodology may be based upon previous work in related catalysis, perhaps 4d metal systems, or simply by using methods that have already been applied in the literature. For example, early computations from the Beller group used B3PW91, based upon the performance of this hybrid functional in previous work (including benchmarking studies) across 3d, 4d and 5d transition metal complexes though more recent work from this group has used the hybrid PBE0 functional [ 9 , 10 , 11 , 12 , 13 , 14 , 15 ].…”

Section: Introductionmentioning

confidence: 99%

Hydricity of 3d Transition Metal Complexes from Density Functional Theory: A Benchmarking Study

Goodfellow

Bühl

2021

Molecules

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A range of modern density functional theory (DFT) functionals have been benchmarked against experimentally determined metal hydride bond strengths for three first-row TM hydride complexes. Geometries were found to be produced sufficiently accurately with RI-BP86-D3(PCM)/def2-SVP and further single-point calculations with PBE0-D3(PCM)/def2-TZVP were found to reproduce the experimental hydricity accurately, with a mean absolute deviation of 1.4 kcal/mol for the complexes studied.

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Exploring the mechanisms of aqueous methanol dehydrogenation catalyzed by defined PNP Mn and Re pincer complexes under base-free as well as strong base conditions

Abstract: The mechanisms of aqueous methanol dehydrogenation reaction catalyzed by defined Mn and Re pincer complexes under different conditions were computed.

Cited by 36 publications

References 71 publications

Cobalt‐Catalyzed Aqueous Dehydrogenation of Formic Acid

Cobalt‐Catalyzed Aqueous Dehydrogenation of Formic Acid

Recent Progress with Pincer Transition Metal Catalysts for Sustainability

Hydricity of 3d Transition Metal Complexes from Density Functional Theory: A Benchmarking Study

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