Recent advancement in oxidation or acceptorless dehydrogenation of alcohols to valorised products using manganese based catalysts

Chandra, Prakash; Ghosh, Topi; Choudhary, Neha; Mohammad, Akbar; Mobin, Shaikh M.

doi:10.1016/j.ccr.2020.213241

Cited by 70 publications

(38 citation statements)

References 292 publications

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“…From catalysis standpoint, the formation of Mn hydride species is generally accepted as a prerequisite for entering the hydrogenation cycle 8 – 13 , 16 – 19 , 29 , 30 , 33 . Our data, on the other hand, indicated that the Mn–H formation from 4 is slow and requires the irreversible loss of one CO ligand.…”

Section: Resultsmentioning

confidence: 99%

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Robust and efficient hydrogenation of carbonyl compounds catalysed by mixed donor Mn(I) pincer complexes

et al. 2021

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Any catalyst should be efficient and stable to be implemented in practice. This requirement is particularly valid for manganese hydrogenation catalysts. While representing a more sustainable alternative to conventional noble metal-based systems, manganese hydrogenation catalysts are prone to degrade under catalytic conditions once operation temperatures are high. Herein, we report a highly efficient Mn(I)-CNP pre-catalyst which gives rise to the excellent productivity (TOF° up to 41 000 h−1) and stability (TON up to 200 000) in hydrogenation catalysis. This system enables near-quantitative hydrogenation of ketones, imines, aldehydes and formate esters at the catalyst loadings as low as 5–200 p.p.m. Our analysis points to the crucial role of the catalyst activation step for the catalytic performance and stability of the system. While conventional activation employing alkoxide bases can ultimately provide catalytically competent species under hydrogen atmosphere, activation of Mn(I) pre-catalyst with hydride donor promoters, e.g. KHBEt3, dramatically improves catalytic performance of the system and eliminates induction times associated with slow catalyst activation.

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Section: Resultsmentioning

confidence: 99%

“…However, the requirements for more sustainable hydrogenation processes recently initiated a search for earth-abundant, inexpensive 3 d metals that can replace their noble counterparts 4 – 7 . In this search, the catalysts based on highly biocompatible and abundant Mn metal became particularly prominent 8 – 13 .…”

Section: Introductionmentioning

confidence: 99%

Robust and efficient hydrogenation of carbonyl compounds catalysed by mixed donor Mn(I) pincer complexes

et al. 2021

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“…The introduction of different auxiliary ligands (halides, carboxylates, alcohols, dicyanamides, thiocyanates, etc.) alters the geometry of the compounds [ 20 , 79 ], giving rise to different behaviors in catalysis. Labile auxiliary ligands or solvent molecules in the axial positions favor catalytic activity through an inner-sphere electron transfer mechanism in which a vacant can be generated in this site, where the substrate molecule can be subsequently accommodated [ 80 ].…”

Section: Manganosalen Complexes As Catalytic Antioxidantsmentioning

confidence: 99%

Pursuing the Elixir of Life: In Vivo Antioxidative Effects of Manganosalen Complexes

et al. 2020

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Manganosalen complexes are coordination compounds that possess a chelating salen-type ligand, a class of bis-Schiff bases obtained by condensation of salicylaldehyde and a diamine. They may act as catalytic antioxidants mimicking both the structure and the reactivity of the native antioxidant enzymes active site. Thus, manganosalen complexes have been shown to exhibit superoxide dismutase, catalase, and glutathione peroxidase activities, and they could potentially facilitate the scavenging of excess reactive oxygen species (ROS), thereby restoring the redox balance in damaged cells and organs. Initial catalytic studies compared the potency of these compounds as antioxidants in terms of rate constants of the chemical reactivity against ROS, giving catalytic values approaching and even exceeding that of the native antioxidative enzymes. Although most of these catalytic studies lack of biological relevance, subsequent in vitro studies have confirmed the efficiency of many manganosalen complexes in oxidative stress models. These synthetic catalytic scavengers, cheaper than natural antioxidants, have accordingly attracted intensive attention for the therapy of ROS-mediated injuries. The aim of this review is to focus on in vivo studies performed on manganosalen complexes and their activity on the treatment of several pathological disorders associated with oxidative damage. These disorders, ranging from the prevention of fetal malformations to the extension of lifespan, include neurodegenerative, inflammatory, and cardiovascular diseases; tissue injury; and other damages related to the liver, kidney, or lungs.

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“…The introduction of different auxiliary ligands (halides, carboxylates, alcohols, dicyanamides, thiocyanates, etc.) alters the geometry of the compounds [20,80], giving rise to different behaviours in catalysis. Labile auxiliary ligands or solvent molecules in the axial positions favour catalytic activity through an inner-sphere electron transfer mechanism in which a vacant can be generated in this site, where the substrate molecule can be subsequently accommodated [81].…”

Section: Manganosalen Complexes As Catalytic Antioxidantsmentioning

confidence: 99%

Pursuing the Elixir of Life: In Vivo Antioxidative Effect of Manganosalen Complexes, a Review

Rouco¹,

Pedrido²,

Maneiro³

2020

Preprint

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Manganosalen complexes are coordination compounds that possess a chelating salen-type ligand, a class of bis-Schiff bases obtained by condensation of salicylaldehyde and a diamine. They may act as catalytic antioxidants mimicking both the structure and the reactivity of the native antioxidant enzymes active site. Thus, manganosalen complexes have shown to exhibit superoxide dismutase, catalase, and glutathione peroxidase activities, and they could potentially facilitate the scavenging of excess ROS, thereby restoring the redox balance in the damaged cells and organs. Initial catalytic studies compared the potency of these compounds as antioxidants in terms of rate constants of the chemical reactivity against ROS, giving catalytic values approaching and even exceeding that of the native antioxidative enzymes. Although most of these catalytic studies lack of biological relevance, subsequent in vitro studies have confirmed the efficiency of many manganosalen complexes in oxidative stress models. These synthetic catalytic scavengers, cheaper than natural antioxidants, have accordingly attracted intensive attention for the therapy of ROS-mediated injuries. The aim of this review is to focus on in vivo studies performed on manganosalen complexes and their activity on the treatment of several pathological disorders associated with oxidative damage. This disorders, ranging from the prevention of fetal malformations to the extension of lifespan, include neurodegenerative, inflammatory and cardiovascular diseases, tissue injury, and other damages related to liver, kidney or lungs.

show abstract

Recent advancement in oxidation or acceptorless dehydrogenation of alcohols to valorised products using manganese based catalysts

Cited by 70 publications

References 292 publications

Robust and efficient hydrogenation of carbonyl compounds catalysed by mixed donor Mn(I) pincer complexes

Robust and efficient hydrogenation of carbonyl compounds catalysed by mixed donor Mn(I) pincer complexes

Pursuing the Elixir of Life: In Vivo Antioxidative Effects of Manganosalen Complexes

Pursuing the Elixir of Life: In Vivo Antioxidative Effect of Manganosalen Complexes, a Review

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