Counterion Effect in Cobaltate‐Catalyzed Alkene Hydrogenation DOI Creative Commons
Martin Gawron, Franziska Gilch,

Daniel Schmidhuber

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 136(6)

Опубликована: Дек. 8, 2023

Abstract We show that countercations exert a remarkable influence on the ability of anionic cobaltate salts to catalyze challenging alkene hydrogenations. An evaluation catalytic properties [Cat][Co(η 4 ‐cod) 2 ] (Cat=K ( 1 ), Na Li 3 Dep nacnac)Mg and N( n Bu) 5 ); cod=1,5‐cyclooctadiene, nacnac={2,6‐Et C 6 H NC(CH )} CH)]) demonstrated lithium salt magnesium drastically outperform other catalysts. Complex was most active catalyst, which readily promotes hydrogenation highly congested alkenes under mild conditions. A plausible mechanism is proposed based density functional theory (DFT) investigations. Furthermore, combined molecular dynamics (MD) simulation DFT studies were used examine turnover‐limiting migratory insertion step. The results these suggest an co‐catalytic role counterion in reaction through coordination cobalt hydride intermediates.

Язык: Английский

Cooperative activation of carbon–hydrogen bonds by heterobimetallic systems DOI Creative Commons
Abdelhak Lachguar, Andrey V. Pichugov, Till Neumann

и другие.

Dalton Transactions, Год журнала: 2023, Номер 53(4), С. 1393 - 1409

Опубликована: Дек. 21, 2023

The activation of C–H bonds by heterobimetallic compounds is a rich area research that has recently received increased attention. This perspective highlights recent advances and aims to guide the reader in this rapidly evolving field.

Язык: Английский

Процитировано

17
Unlocking the Metalation Applications of TMP‐powered Fe and Co(II) bis(amides): Synthesis, Structure and Mechanistic Insights DOI Creative Commons
Alessandra Logallo, Lewis C. H. Maddock, Manting Mu

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(24)

Опубликована: Апрель 2, 2024

Abstract Typified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6‐tetramethylpiperidide), s‐block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition lack sufficient basicity to activate these substrates. Breaking new ground this field, here we present synthesis full characterisation of earth‐abundant metals M(TMP) 2 (M=Fe, Co). Uncovering a reactivity profile towards fluoroarenes, amide complexes can promote direct M−H exchange processes regioselectively using one or two their basic arms. Remarkably, even when perfluorinated substrate, selective C‐H metalation occurs leaving C−F bonds intact. Their kinetic be boosted LiCl NBu 4 Cl additives which enables formation kinetically activated ate species. Combining spectroscopic structural studies with DFT calculations, mechanistic insights been gained on how low polarity take place. also used access ferrocene cobaltocene deprotonation cyclopentadiene undergo efficient CO insertion both groups under mild reaction conditions.

Язык: Английский

Процитировано

4
Counterion Effect in Cobaltate‐Catalyzed Alkene Hydrogenation DOI Creative Commons
Martin Gawron, Franziska Gilch,

Daniel Schmidhuber

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(6)

Опубликована: Дек. 8, 2023

We show that countercations exert a remarkable influence on the ability of anionic cobaltate salts to catalyze challenging alkene hydrogenations. An evaluation catalytic properties [Cat][Co(η

Язык: Английский

Процитировано

6
Unlocking the Metalation Applications of TMP‐powered Fe and Co(II) bis(amides): Synthesis, Structure and Mechanistic Insights DOI Creative Commons
Alessandra Logallo, Lewis C. H. Maddock, Manting Mu

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(24)

Опубликована: Апрель 2, 2024

Abstract Typified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6‐tetramethylpiperidide), s‐block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition lack sufficient basicity to activate these substrates. Breaking new ground this field, here we present synthesis full characterisation of earth‐abundant metals M(TMP) 2 (M=Fe, Co). Uncovering a reactivity profile towards fluoroarenes, amide complexes can promote direct M−H exchange processes regioselectively using one or two their basic arms. Remarkably, even when perfluorinated substrate, selective C‐H metalation occurs leaving C−F bonds intact. Their kinetic be boosted LiCl NBu 4 Cl additives which enables formation kinetically activated ate species. Combining spectroscopic structural studies with DFT calculations, mechanistic insights been gained on how low polarity take place. also used access ferrocene cobaltocene deprotonation cyclopentadiene undergo efficient CO insertion both groups under mild reaction conditions.

Язык: Английский

Процитировано

1
Structural and Reactivity Implications of Homo- and Heterobimetallic Co(II) Amides Prepared via Trans(amination) Reactions DOI

Na Jin,

Alessandra Logallo, Eva Hevia

и другие.

Organometallics, Год журнала: 2024, Номер 44(1), С. 197 - 206

Опубликована: Дек. 3, 2024

Язык: Английский

Процитировано

1
Interaction and Energy Decomposition Analyses to Predict Stability of Tetraaryl Square Planar Cobalt Complexes DOI Creative Commons
Manting Mu, Alessandra Logallo, Eva Hevia

и другие.

ChemCatChem, Год журнала: 2023, Номер 15(19)

Опубликована: Июль 26, 2023

Abstract The sodium‐mediated cobaltation of pentafluorobenzene using the bimetallic base [NaCo(HMDS) 3 ] (HMDS=N(SiMe ) 2 has been reported to afford a novel tetraaryl Co(II) square planar complex. Yet, preparation analogue structures with 1,2,3,4‐tetrafluorobenzene, 1,3,5‐trichlorobenzene, and 1,4‐dibromo‐2,5‐difluorobenzene remains elusive. While metalation step proceeds leading stable Ar] species, ligand redistribution process complexes does not take place. Herein we report density functional theory study in combination electronic structure energy decomposition analyses shed light on steric requirements such complexes. Our findings show that formation depends right balance between intramolecular X⋅⋅⋅X Na⋅⋅⋅X (X=H, F, Cl, Br) interactions. latter further induces ‘seesaw effect’ , whereby aryl acts as ‘seesaw’ allowing two X atoms ortho positions interdependently interact Na. Only by considering both attractive repulsive Na(X)⋅⋅⋅X interactions, correct stability observed experiments can be predicted computationally. We envision these insights guide rational design metal for C−C coupling, field is still dominated scarce expensive precious metals.

Язык: Английский

Процитировано

3
Counterion Effect in Cobaltate‐Catalyzed Alkene Hydrogenation DOI Creative Commons
Martin Gawron, Franziska Gilch,

Daniel Schmidhuber

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 136(6)

Опубликована: Дек. 8, 2023

Abstract We show that countercations exert a remarkable influence on the ability of anionic cobaltate salts to catalyze challenging alkene hydrogenations. An evaluation catalytic properties [Cat][Co(η 4 ‐cod) 2 ] (Cat=K ( 1 ), Na Li 3 Dep nacnac)Mg and N( n Bu) 5 ); cod=1,5‐cyclooctadiene, nacnac={2,6‐Et C 6 H NC(CH )} CH)]) demonstrated lithium salt magnesium drastically outperform other catalysts. Complex was most active catalyst, which readily promotes hydrogenation highly congested alkenes under mild conditions. A plausible mechanism is proposed based density functional theory (DFT) investigations. Furthermore, combined molecular dynamics (MD) simulation DFT studies were used examine turnover‐limiting migratory insertion step. The results these suggest an co‐catalytic role counterion in reaction through coordination cobalt hydride intermediates.

Язык: Английский

Процитировано

1