Stereoselective Semi‐Hydrogenations of Alkynes by First‐Row (3d) Transition Metal Catalysts

Gregori, Bernhard J.; Wangelin, Axel Jacobi von; Schmotz, Mattis-Ole W. S.

doi:10.1002/cctc.202200886

Cited by 23 publications

(11 citation statements)

References 251 publications

(291 reference statements)

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“…Achieving stereo‐chemical control in this reaction is a long‐standing challenge and continues to be the subject of intensive investigation [84] . Nevertheless, appreciable progress has been made in this direction by applying 3d base metal‐based catalysts [85] …”

Section: Hydrogenation Reactions Using Cr Mo and Wmentioning

confidence: 99%

Advances in Group VI Metal‐Catalyzed Homogeneous Hydrogenation and Dehydrogenation Reactions

Singh,

Atreya,

Jalwal

et al. 2023

Chemistry An Asian Journal

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Transition metal‐catalyzed homogeneous hydrogenation and dehydrogenation reactions for attaining plethora of organic scaffolds have evolved as a key domain of research in academia and industry. These protocols are atom‐economic, greener, in line with the goal of sustainability, eventually pave the way for numerous novel environmentally benign methodologies. Appealing progress has been achieved in the realm of homogeneous catalysis utilizing noble metals. Owing to their high cost, less abundance along with toxicity issues led the scientific community to search for sustainable alternatives. In this context, earth‐ abundant base metals have gained substantial attention culminating enormous progress in recent years, predominantly with pincer‐type complexes of nickel, cobalt, iron, and manganese. In this regard, group VI chromium, molybdenum and tungsten complexes have been overlooked and remain underdeveloped despite their earth‐abundance and bio‐compatibility. This review delineates a comprehensive overview in the arena of homogeneously catalysed (de)hydrogenation reactions using group VI base metals chromium, molybdenum, and tungsten till date. Various reactions have been described; hydrogenation, transfer hydrogenation, dehydrogenation, acceptorless dehydrogenative coupling, hydrogen auto transfer, along with their scope and brief mechanistic insights.

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Section: Hydrogenation Reactions Using Cr Mo and Wmentioning

confidence: 99%

Advances in Group VI Metal‐Catalyzed Homogeneous Hydrogenation and Dehydrogenation Reactions

Singh,

Atreya,

Jalwal

et al. 2023

Chemistry An Asian Journal

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“…For instance, it was recently discovered that Mn−PR 2 moieties are reactive toward H 2 and, [29] intriguingly, that cis ‐vinyl inserted Mn(I) intermediate complexes react with H 2 to form a trans ‐alkene product, exclusively, without cis to trans isomerization [30] . This selectivity mode is in contrast to the normal cis to trans isomerization mode in mononuclear catalysts [12,31] . It was further demonstrated that the catalytic platform can be assembled in situ directly from Mn 2 (CO) 10 and phosphine (R 2 PH) without the need for isolation.…”

Section: Introductionmentioning

confidence: 97%

Dinuclear Mn(I) Complexes with Phosphido and Hydrido Bridges: Synthesis, Reactivity, and Hydrogenative Catalysis

Lacy

Abhyankar

2023

Chemistry A European J

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A class of organomanganese hydrogenation catalysts was recently rediscovered. These are simple dinuclear Mn(I) carbonyl compounds with phosphido (PR 2 À ) and hydrido (H À ) bridges. This class of compounds has been known since the 1960's, and they have rich coordination chemistry and reactivity. Given their recently discovered potential for catalytic applications, a fresh look at this class of compounds was necessary. Hence, this Review comprehensively covers the synthesis, reactivity, and catalysis of this interesting class of molecules.

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“…The catalytic relevance of this cooperative mechanism is demonstrated in the selective semihydrogenation of diphenylacetylene to Z- stilbene under mild conditions, with a comparable performance to recently disclosed Ni-based systems. 5,[43][44][45][46][47]…”

Section: Introductionmentioning

confidence: 99%

Cooperative H2 Activation at a Nickel(0)-Olefin Center

Sansores-Paredes

Lutz

Moret

2023

Preprint

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Catalytic olefin hydrogenation reactions are ubiquitous in organic synthesis. Most proposed catalytic cycles for the homogeneous hydrogenation of olefins using molecular H2 start with the oxidative addition of H2 by metal complexes to form two reactive M–H bonds, often via a non-classical metal dihydrogen (M–H2) intermediate. Previous reports had provided indirect evidence for an alternative mechanism involving direct hydrogen transfer from a metal-bound H2 molecule to a metal-bound olefin without the oxidative addition step. However, the key metal(olefin)(H2) and the corresponding ligand-to-ligand hydrogen transfer (LLHT) step had not been directly observed. Herein, we show that incorporating a precoordinated olefin in a P(C=C)P pincer ligand framework allows for the observation of both a non-classical Ni-(H2) complex and the Ni(alkyl)(hydrido) product of LLHT in rapid equilibrium with dissolved H2. The utility of this cooperative H2-activation mechanism for catalysis is demonstrated in the semihydrogenation of diphenylacetylene under mild conditions. Mechanistic investigations supported by DFT calculations back the central role of LLHT for both cooperative H2 activation and catalytic semihydrogenation. These results provide an experimental basis for the role of LLHT steps in olefin hydrogenation mechanisms and demonstrate the utility of olefin-based pincer ligands for cooperative catalysis with non-noble metals.

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Stereoselective Semi‐Hydrogenations of Alkynes by First‐Row (3d) Transition Metal Catalysts

Abstract: Dedicated to Matthias Beller on the occasion of his 60 th birthdayChemCatChem www.chemcatchem.org

Cited by 23 publications

References 251 publications

Advances in Group VI Metal‐Catalyzed Homogeneous Hydrogenation and Dehydrogenation Reactions

Advances in Group VI Metal‐Catalyzed Homogeneous Hydrogenation and Dehydrogenation Reactions

Dinuclear Mn(I) Complexes with Phosphido and Hydrido Bridges: Synthesis, Reactivity, and Hydrogenative Catalysis

Cooperative H2 Activation at a Nickel(0)-Olefin Center

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