A Density Functional Study of the Hydrogenation of Ketones Catalysed by Neutral Rhodium‐Diphosphane Complexes

Agbossou‐Niedercorn, Francine; Paul, Jean‐François

doi:10.1002/ejic.200600299

Cited by 10 publications

(3 citation statements)

References 58 publications

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“…An overview of viable catalytic cycles: In addition to the mechanisms postulated by Ojima and Chan, mechanistic pathways involving alkoxy intermediates like those found in hydrogenation reactions, [49] analogues to Chalk-Harrod [12] or modified Chalk-Harrod mechanisms, [50] or double oxidative adducts of silane were investigated. Since the catalytic reactions have been usually performed with low catalyst loadings, the formation of dinuclear rhodium complexes was ruled out.…”

Section: Resultsmentioning

confidence: 99%

Multiple Reaction Pathways in Rhodium‐Catalyzed Hydrosilylations of Ketones

Schneider¹,

Finger²,

Haferkemper³

et al. 2009

Chemistry A European J

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A detailed density functional theory (DFT) computational study (using the BP86/SV(P) and B3LYP/TZVP//BP86/SV(P) level of theory) of the rhodium-catalyzed hydrosilylation of ketones has shown three mechanistic pathways to be viable. They all involve the generation of a cationic complex [L(n)Rh(I)]+ stabilized by the coordination of two ketone molecules and the subsequent oxidative addition of the silane, which results in the Rh-silyl intermediates [L(n)Rh(III)(H)SiHMe2]+. However, they differ in the following reaction steps: in two of them, insertion of the ketone into the Rh-Si bond occurs, as previously proposed by Ojima et al., or into the Si-H bond, as proposed by Chan et al. for dihydrosilanes. The latter in particular is characterized by a very high activation barrier associated with the insertion of the ketone into the Si-H bond, thereby making a new, third mechanistic pathway that involves the formation of a silylene intermediate more likely. This "silylene mechanism" was found to have the lowest activation barrier for the rate-determining step, the migration of a rhodium-bonded hydride to the ketone that is coordinated to the silylene ligand. This explains the previously reported rate enhancement for R2SiH2 compared to R3SiH as well as the inverse kinetic isotope effect (KIE) observed experimentally for the overall catalytic cycle because deuterium prefers to be located in the stronger bond, that is, C-D versus M-D.

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Section: Resultsmentioning

confidence: 99%

Multiple Reaction Pathways in Rhodium‐Catalyzed Hydrosilylations of Ketones

Schneider¹,

Finger²,

Haferkemper³

et al. 2009

Chemistry A European J

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“…(2) The s-trans (E)-enamine (27), is the preferred conformation due to a steric interaction between the acid group and the b-hydrogen in the alternative s-cis (28).…”

Section: Organocatalysis Enamine Organocatalysismentioning

confidence: 99%

“…Agbossou-Niedercorn and Paul have used DFT studies (B3LYP with double-z quality basis sets) to consider the mechanism of ketone hydrogenation catalysed by neutral rhodium-diphosphane complexes. 27 In their own experimental program they have compared reactions using cationic complexes such as [Rh(COD) 2 ]BF 4 (74) (COD = 1,5 cyclooctadiene) and the neutral species [Rh(COD)Cl] 2 (75), as precatalysts. Chirality is introduced here through bidentate aminophosphane phosphinite ligands (AMPP) of which the most successful has been (S)-Cp s ,Cp s -oxo-ProNOP (76).…”

Section: Enantioselective Catalysismentioning

confidence: 99%

Catalysis: experimental and computational

Willock

2007

Annu. Rep. Prog. Chem., Sect. B: Org. Chem.

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Heterostructured Catalytic Materials as Advanced Electrocatalysts: Classification, Synthesis, Characterization, and Application

Wu,

Yan,

Wang

et al. 2024

Adv Funct Materials

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The proactive exploration of electrocatalytic conversion for renewable energy valorization is of tremendous significance in addressing the issues of fossil energy exhaustion, among which the critical challenge of electrocatalysis lies in the rational design of efficient electrocatalysts that are rich in the earth. Among electrocatalysts, the design of heterostructured materials exhibits immense potential for the optimization of noble metals and elaboration of non‐precious metal electrocatalysts with durability. In this review, a systematic overview of modern advances in heterostructured electrocatalysts for a range of energy conversion reactions is described, and special interfacial design brings additional functional effects. Subsequently, various synthesis methods and characterization techniques for heterostructured electrocatalysts are also summarized. The innovative classification of heterostructures in methods of interfacial junction, crystal structure, structural morphology, and properties of the components is presented in this review. Finally, the possible challenges and outlooks of heterostructured electrocatalysts in the future are further discussed, including how to develop more sophisticated synthesis, characterization, and theoretical calculation methods, which will serve as the guiding direction for a more rational interface design. This review aims to set the trajectory for providing meaningful inspiration and references in energy conversion by heterostructured electrocatalysts, advancing the process of carbon neutrality.

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A Density Functional Study of the Hydrogenation of Ketones Catalysed by Neutral Rhodium‐Diphosphane Complexes

Cited by 10 publications

References 58 publications

Multiple Reaction Pathways in Rhodium‐Catalyzed Hydrosilylations of Ketones

Multiple Reaction Pathways in Rhodium‐Catalyzed Hydrosilylations of Ketones

Catalysis: experimental and computational

Heterostructured Catalytic Materials as Advanced Electrocatalysts: Classification, Synthesis, Characterization, and Application

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