Two step activation of Ru-PN<sup>3</sup>P pincer catalysts for CO<sub>2</sub> hydrogenation

Tossaint, Alex S.; Rebreyend, Christophe; Sinha, Vivek; Weber, Manuela; Canossa, Stefano; Pidko, Evgeny A.; Filonenko, Georgy A.

doi:10.1039/d2cy00485b

Cited by 12 publications

(4 citation statements)

References 36 publications

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“…These results are perfectly in line with well‐known superior hydricity of anionic transition metal complexes vs . their neutral congeners estimated either experimentally [42a,d,47] or by theoretical means [42a–b,45] …”

Section: Resultsmentioning

confidence: 99%

Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation

Gulyaeva,

Buhaibeh,

Boundor

et al. 2024

Chemistry A European J

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Systematic modification of the chelating NHC‐phosphine ligand (NHC = N‐heterocyclic carbene) in highly efficient ketone hydrogenation Mn(I) catalyst fac‐[(Ph2PCH2NHC)Mn(CO)3Br] has been performed and the catalytic activity of the resulting complexes was evaluated using acetophenone as a benchmark substrate. While the variation of phosphine and NHC moieties led to inferior results than for a parent system, the incorporation of a phenyl substituent into the ligand methylene bridge improved catalytic performance by ca. 3 times providing maximal TON values in the range of 15000‐20000. Mechanistic investigation combining experimental and computational studies allowed to rationalize this beneficial effect as an enhanced stabilization of reaction intermediates including anionic hydride species fac‐[(Ph2PC(Ph)NHC)Mn(CO)3H]− playing a crucial role in the hydrogenation process. These results highlight the interest of such carbon bridge substitution strategy being rarely employed in the design of chemically non‐innocent ligands.

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Section: Resultsmentioning

confidence: 99%

Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation

Gulyaeva,

Buhaibeh,

Boundor

et al. 2024

Chemistry A European J

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“…To illustrate the practical capabilities and potential of the MACE methodology, we considered a model system of Ru-PN 3 P pincer complex, for which the structure has been resolved and which has earlier been used as a catalyst for CO 2 and bicarbonate hydrogenation. , X-ray crystal structure gives an unambiguous solution to the structural problem of coordination complexes by providing a global minimum configuration in the solid state.…”

Section: Applicationsmentioning

confidence: 99%

MACE: Automated Assessment of Stereochemistry of Transition Metal Complexes and Its Applications in Computational Catalysis

Chernyshov,

Pidko

2024

J. Chem. Theory Comput.

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Computational chemistry pipelines typically commence with geometry generation, well-established for organic compounds but presenting a considerable challenge for transition metal complexes. This paper introduces MACE, an automated computational workflow for converting chemist SMILES/MOL representations of the ligands and the metal center to 3D coordinates for all feasible stereochemical configurations for mononuclear octahedral and square planar complexes directly suitable for quantum chemical computations and implementation in high-throughput computational chemistry workflows. The workflow is validated through a structural screening of a data set of transition metal complexes extracted from the Cambridge Structural Database. To further illustrate the power and capabilities of MACE, we present the results of a model DFT study on the hemilability of pincer ligands in Ru, Fe, and Mn complexes, which highlights the utility of the workflow for both focused mechanistic studies and larger-scale high-throughput pipelines.

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“…[9] Another interesting approach is direct reduction of bicarbonate to formate since CO 2 remains in equilibrium with bicarbonate in aqueous medium. [6,10] Also, bicarbonates are easily formed from CO 2 and alkanol amines. Such hydrogenation reactions have been studied predominantly using homogeneous catalysts such as noble metal (e. g. Ru, Rh and Ir) complexes in batch reactors under high pressure conditions (~60-100 bar).…”

Section: Introductionmentioning

confidence: 99%

“…Many basic additives such as KOH and NaHCO 3 are used to promote the reaction and overcome the thermodynamic limitations (equation 2) [9] . Another interesting approach is direct reduction of bicarbonate to formate since CO 2 remains in equilibrium with bicarbonate in aqueous medium [6,10] . Also, bicarbonates are easily formed from CO 2 and alkanol amines.…”

Section: Introductionmentioning

confidence: 99%

Liquid‐Liquid‐Gas Triphasic Hydrogenation of Bicarbonate to Formate in a Continuous Flow Tubular Reactor

Afreen,

Bansode,

Wada

et al. 2024

Adv Synth Catal

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Multiphasic reaction of bicarbonate hydrogenation to form formate using homogeneous Ru PNP pincer catalyst in a continuous flow tubular reactor is reported. The reaction system consists of three phases. Catalyst is dissolved in toluene while bicarbonate is dissolved in water. The significance of efficient mixing among the organic phase, aqueous phase and gaseous hydrogen to improve hydrogenation reaction by using different inert packing materials is studied by operando visualisation and also quantitatively discussed. The bicarbonate conversion of up to 67% is achieved after optimisation of important reaction and reactor parameters. The designed reactor setup comprised of effective recycling system that recycles the catalyst with >99% activity.

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Two step activation of Ru-PN³P pincer catalysts for CO₂ hydrogenation

Abstract: Activation of homogeneous catalysts is an important step in ensuring efficient operation of any catalytic system as a whole. For the majority of pincer catalysts, the activation step leans heavily...

Cited by 12 publications

References 36 publications

Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation

Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation

MACE: Automated Assessment of Stereochemistry of Transition Metal Complexes and Its Applications in Computational Catalysis

Liquid‐Liquid‐Gas Triphasic Hydrogenation of Bicarbonate to Formate in a Continuous Flow Tubular Reactor

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Two step activation of Ru-PN3P pincer catalysts for CO2 hydrogenation

Abstract: Activation of homogeneous catalysts is an important step in ensuring efficient operation of any catalytic system as a whole. For the majority of pincer catalysts, the activation step leans heavily...

Cited by 12 publications

References 36 publications

Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation

Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation

MACE: Automated Assessment of Stereochemistry of Transition Metal Complexes and Its Applications in Computational Catalysis

Liquid‐Liquid‐Gas Triphasic Hydrogenation of Bicarbonate to Formate in a Continuous Flow Tubular Reactor

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Two step activation of Ru-PN³P pincer catalysts for CO₂ hydrogenation