Aldehyde Binding through Reversible C–C Coupling with the Pincer Ligand upon Alcohol Dehydrogenation by a PNP–Ruthenium Catalyst

Montag, Michael; Zhang, Jing; Milstein, David

doi:10.1021/ja303121v

Cited by 139 publications

(140 citation statements)

References 48 publications

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“…[31,32] Based on our computational results, we assumed that this process occurs in a single step (via TS) resulting in open-1 (involved in a rapid exchange with the other forms of 1). [31,32] Based on our computational results, we assumed that this process occurs in a single step (via TS) resulting in open-1 (involved in a rapid exchange with the other forms of 1).…”

Section: Methodsmentioning

confidence: 99%

Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H₂ Addition and Kinetic Analysis

et al. 2014

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Ansa-aminoborane 1 (ortho-TMP-C6H4-BH2; TMP = 2,2,6,6-tetramethylpiperid-1-yl), a frustrated Lewis pair with the smallest possible Lewis acidic boryl site (-BH2), is prepared. Although it is present in quenched forms in solution, and BH2 represents an acidic site with reduced hydride affinity, 1 reacts with H2 under mild conditions producing ansa-ammonium trihydroborate 2. The thermodynamic and kinetic features as well as the mechanism of this reaction are studied by variable-temperature NMR spectroscopy, spin-saturation transfer experiments, and DFT calculations, which provide comprehensive insight into the nature of 1.

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Section: Methodsmentioning

confidence: 99%

Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H₂ Addition and Kinetic Analysis

et al. 2014

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“…Alcohol dehydrogenation : In the area of alcohol dehydrogenation, extensive studies have been performed by the groups of Baratta,91 Gelman,92 Milstein,9, 93 Szymczak,11 Koridze,94 Hanson,76 and Jones and Schneider 60. To be more precise, in 2011 Baratta et al.…”

Section: Catalysis With Pincer‐type Catalystsmentioning

confidence: 99%

Pincer‐Type Complexes for Catalytic (De)Hydrogenation and Transfer (De)Hydrogenation Reactions: Recent Progress

Werkmeister

Neumann

Junge

et al. 2015

Chemistry A European J

337

144

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Pincer complexes are becoming increasingly important for organometallic chemistry and organic synthesis. Since numerous applications for such catalysts have been developed in recent decades, this Minireview covers progress in their use as catalysts for (de)hydrogenation and transfer (de)hydrogenation reactions during the last four years. Aside from noble-metal-based pincer complexes, the corresponding base metal complexes are also highlighted and their applications summarized.

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“…Moreover, Milstein and coworkers indicated in their experimental study that the β-H elimination mechanism does not occur in the alcohol dehydrogenation. 63 Scheme 14: Proposed mechanisms for the alcohol dehydrogenation via bifunctional double hydrogen transfer mechanism (in green) and β-H elimination mechanism (in red) in toluene with the TPSS by Wang and coworkers (values are free energies). 42 The coupling reactions between aldehyde and amine or alcohol to form hemiaminal 64 or hemiacetal 65 were mediated by alcohol that is used to bridge the proton transfer gap.…”

Section: Mechanisms For the Dehydrogenative Coupling Reactionsmentioning

confidence: 99%

Computational Mechanistic Studies on Reactions of Transition Metal Complexes with Noninnocent Pincer Ligands: Aromatization–Dearomatization or Not

Hall

2015

ACS Catal.

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The development of green chemistry has attracted the chemists' attentions in recent years. Among them, Milstein and coworkers have discovered a new mode of metal-ligand cooperation in complexes, where an aromatization-dearomatization process of the pyridine or acridine-based PNP and PNN "pincer" ligands appears to be a key element. These complexes were reported to lead to unusual X-H (X=H, C, O, N, and B) activation reactions and to environmentally benign catalysis involving dehydrogenative coupling reactions and hydrogenation reactions, representing an important development in green chemistry. This review provides a summary of theoretical studies on the mechanisms of the reactions mediated by transition metal complexes with noninnocent pincer ligands synthesized by Milstein and coworkers. The aromatization-dearomatization process of the pyridine or acridine-based PNP and PNN "pincer" ligands were found to play important roles in some reactions, while other reactions do not involve the aromatization-dearomatization process. For some reactions, several research groups proposed different mechanisms to explain the same reaction. Thus, to compare these mechanisms, we recalculate their rate-determining steps by using the functionals that are calibrated to produce results close to those from coupled cluster calculations. Moreover, the understanding of the reaction mechanisms can help researchers to improve the current reactions and design new reactions.

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Aldehyde Binding through Reversible C–C Coupling with the Pincer Ligand upon Alcohol Dehydrogenation by a PNP–Ruthenium Catalyst

Cited by 139 publications

References 48 publications

Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H₂ Addition and Kinetic Analysis

Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H₂ Addition and Kinetic Analysis

Pincer‐Type Complexes for Catalytic (De)Hydrogenation and Transfer (De)Hydrogenation Reactions: Recent Progress

Computational Mechanistic Studies on Reactions of Transition Metal Complexes with Noninnocent Pincer Ligands: Aromatization–Dearomatization or Not

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Aldehyde Binding through Reversible C–C Coupling with the Pincer Ligand upon Alcohol Dehydrogenation by a PNP–Ruthenium Catalyst

Cited by 139 publications

References 48 publications

Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H2 Addition and Kinetic Analysis

Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H2 Addition and Kinetic Analysis

Pincer‐Type Complexes for Catalytic (De)Hydrogenation and Transfer (De)Hydrogenation Reactions: Recent Progress

Computational Mechanistic Studies on Reactions of Transition Metal Complexes with Noninnocent Pincer Ligands: Aromatization–Dearomatization or Not

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Product

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Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H₂ Addition and Kinetic Analysis

Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H₂ Addition and Kinetic Analysis