Transition metal catalysts for the hydrogenation of carbon dioxide to value added materials DOI Open Access

Clayton Hert

Published: Aug. 1, 2023

Over the last several years field of CO2 hydrogenation has become robust and is still growing. There great deal interest into sector as new ligands, catalysts, systems are published regularly which help us further understand intricacies reaction how we might improve it for future use. This work first analyzes current catalysts employable carbon dioxide to formates, formamides, methanol. We produced a iPrPNPhP ligand derived from commonly used ligands iPrPNMeP iPrPNHP. these isolate characterize series ruthenium hydride complexes demonstrated their very different catalytic ability formic acid dehydrogenation formate. furthered our labs previous on increased reactivity non metal cooperative mechanism Lewis assisted formate with manganese pincer complexes. The matched those previously seen iron, mechanistic studies were performed elucidate effect non-metal mechanisms have catalyst activity. Lastly report synthetic progress towards phospholane bear ligand. Success was had in isolating system though underway its catalysis.

Language: Английский

Unlocking the potential of metal ligand cooperation for enantioselective transformations DOI Creative Commons
Tizian‐Frank Ramspoth, Johanan Kootstra, Syuzanna R. Harutyunyan

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(7), P. 3216 - 3223

Published: Jan. 1, 2024

Metal–ligand cooperation, (MLC) is a versatile catalysis concept. Herein, we discuss the historical context, mechanisms, and applications, suggesting exploring MLC for enantioselective transformations beyond (de)hydrogenative processes.

Language: Английский

Citations

11
Hydrogen Borrowing Catalysis for the Modification, Depolymerization, and Synthesis of Polyesters DOI Creative Commons
Frederik Rummel, Afiq Anuar, Qiang Yu

et al.

Macromolecules, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 26, 2025

Language: Английский

Citations

0
Understanding the Influence of Lewis Acids on CO2 Hydrogenation: The Critical Effect Is on Formate Rotation DOI Creative Commons
Ljiljana Pavlovic, Kathrin H. Hopmann

Organometallics, Journal Year: 2023, Volume and Issue: 42(20), P. 3025 - 3035

Published: Oct. 11, 2023

Lewis acids (LAs) have been shown to accelerate hydrogenation of CO2, but the underlying mechanistic details remain be elucidated. We employed computational methods investigate how LAs affect CO2 with a range known metal-hydrides (LnIr–H, LnRu–H, LnMn–H, LnCo–H). Our results show that can alter nature hydride–CO2 bond formation step, do not lower its barrier. Instead, accelerating effect is on subsequent rearrangement metal-formate σ-intermediate. These insights are essential for understanding LA additives metal-mediated hydrogenations CO2.

Language: Английский

Citations

9
Kinetic Isotope Effects and the Mechanism of CO2 Insertion into the Metal-Hydride Bond of fac-(bpy)Re(CO)3H DOI

Mariam Barakat,

Sarah Elhajj,

Riyad Yazji

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(26), P. 12133 - 12145

Published: June 20, 2024

The 1,2-insertion reaction of CO2 into metal–hydride bonds d6-octahedral complexes to give κ1-O-metal-formate products is the key step in various reduction schemes and as a result has attracted extensive mechanistic investigations. For many octahedral catalysts, insertion follows an associative mechanism which interacts directly with coordinated hydride ligand instead more classical dissociative that opens empty coordination site bind substrate metal prior migration step. To better understand mechanism, we conducted systematic quantum chemical investigation on between fac-(bpy)Re(CO)3H (1–Re–H; bpy = 2,2′-bipyridine) starting gas phase then moving THF other solvents increased dielectric constants. Detailed analyses potential energy surfaces (PESs) intrinsic coordinates (IRCs) reveal enabled all media by initial stage making 3c-2e bond carbon metal-hydride most consistent organometallic bridging Re–H–CO2 species. Once bent anchored bond, proceeds rotation motion via cyclic transition state TS2 interchanges Re–O–CHO coordination. combined stages provide asynchronous–concerted pathway for Gibbs free surface highest point. Consideration rate-determining TS gives activation barriers, inverse KIEs, substituent effects, solvent effects agree experimental data available this system. An important new insight revealed results not transfer been assumed some studies. In fact, loose vibration can be identified first solution (TS1) does involve Re–H stretching vibrational mode. Accordingly, imaginary frequency TS1 insensitive deuteration, therefore, leads no significant KIE.

Language: Английский

Citations

2
Synthesis, Characterization, and Reactivity of a (PPP) Pincer-Ligated Manganese Carbonyl Complex: Polarity Reversal Imparted by the Electrophilic Nature of a Planar Mn-P(NR2)2 Fragment DOI

Leah K. Oliemuller,

Curtis E. Moore, Christine M. Thomas

et al.

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(34), P. 13997 - 14009

Published: Aug. 16, 2023

The bonding interactions of a synthesized pincer-ligated manganese dicarbonyl complex featuring an N-heterocyclic phosphenium (NHP+) central moiety are explored. pincer ligand [PPP]Cl was coordinated to center using Mn(CO)5Br and 254 nm light afford the chlorophosphine (PPClP)Mn(CO)2Br (2) as mixture halide exchange products stereoisomers. target species (PPP)Mn(CO)2 (3) prepared by treatment 2 with equiv reductant KC8. Computational investigations analysis structural parameters were used elucidate multiple between Mn PNHP atom in 3. generation product formal H2 addition, (PPHP)Mn(CO)2H (4), achieved through dehydrogenation NH3BH3, affording 2:1 4syn:4anti nucleophilic nature electrophilic demonstrated hydride addition protonation 3 produce K(THF)2[(PPHP)Mn(CO)2] (6) (PPClP)Mn(CO)2H (5), respectively. observed reactivity suggests that is best described Mn-I/NHP+ complex, contrast analogues typically assigned MnI species.

Language: Английский

Citations

4
Carbon Dioxide Hydrogenation to Formate Catalyzed by a Neutral, Coordinatively Saturated Tris‐Carbonyl Mn(I)‐PNP Pincer‐Type Complex DOI Creative Commons
Sylwia Kostera, Gabriele Manca, Luca Gonsalvi

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(70)

Published: Sept. 18, 2023

CO2 catalytic hydrogenation to formate was achieved (TONmax =ca. 3800) in the presence of neutral, halide-free, coordinatively saturated tris(carbonyl) manganese pincer-type complex [Mn(PNP)(CO)3 ], bearing a diarylamido PNP ligand, using DBU as base and LiOTf Lewis acid additive, under mild reaction conditions (60 bar, 80 °C). DFT calculations suggest that precatalyst activation key step occurs by intermolecular, assisted dihydrogen heterolytic splitting rather than expected ligand-assisted intramolecular MLC-type mechanism.

Language: Английский

Citations

4
A phosphine-free molecularly-defined Ni(II) complex in catalytic hydrogenation of CO2 DOI

Ritu Bhardwaj,

Joyanta Choudhury

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(74), P. 10176 - 10179

Published: Jan. 1, 2024

The development of base metal catalysts capable CO

Language: Английский

Citations

1
PCP Pincer Complexes of Titanium in the +3 and +4 Oxidation States DOI Creative Commons
Benedek Stadler,

Hilary Meng,

Sara Belazregue

et al.

Organometallics, Journal Year: 2023, Volume and Issue: 42(12), P. 1278 - 1285

Published: March 13, 2023

Ti(IV) and Ti(III) complexes using the

Language: Английский

Citations

3
Activated Mn‐MACHO Complexes Form Stable CO2 Adducts DOI Creative Commons
Ajeet Singh, Gregor Kemper, Thomas Weyhermüller

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(9)

Published: Nov. 30, 2023

Manganese(I) carbonyl complexes bearing a MACHO-type ligand (HN(CH

Language: Английский

Citations

2
Manganese(I) Catalyzed CO2 Reduction Processes in Homogenous Phase DOI Creative Commons
Sylwia Kostera, Luca Gonsalvi

ChemCatChem, Journal Year: 2023, Volume and Issue: 16(7)

Published: Dec. 8, 2023

Abstract The catalytic activation of carbon dioxide (CO 2 ) can be a promising tool for the use this abundant, non‐flammable and non‐toxic gas as feedstock C1 chemical synthesis, in particular bulk products such formic acid (HCOOH) methanol (CH 3 OH). key successful, widespread CO is design application efficient, thermally robust cheap catalysts. In last decade, earth‐abundant transition metal complexes, those 3d metals, has shown results. review article, comprehensive summary main systems described literature homogeneous Mn(I)‐catalyzed reduction processes (hydrogenation, hydroboration hydrosilylation) will described, with attention to effect stabilizing ligands, reaction conditions need additives, together mechanistic details often obtained by combination experimental data DFT calculations.

Language: Английский

Citations

1