A Blueprint for Secondary Coordination Sphere Editing: Approaches Toward Lewis‐Acid Assisted Carbon Dioxide Co‐Activation

ChemSusChem, Journal Year: 2024, Volume and Issue: 17(13)

Published: Feb. 15, 2024

Abstract Carbon dioxide (CO 2 ) is a potent greenhouse gas of environmental concern. Seeking to offer solution the “CO ‐problem”, chemistry community has turned focus toward transition metal complexes which can activate, reduce, and convert CO into carbon‐based products. The design such systems involves judicious selection both accompanying donor ligand; in part, these efforts are motivated by biological metalloenzymes that undertake similar transformations. As element, metal‐ligand cooperativity, leverages intramolecular interactions between an adjacent secondary ligand site, been acknowledged as vitally important component activation community. These “push‐pull” style where electron density chaperoned onto with electrophile, Lewis‐acid, playing role acceptor. This pairing allows for stabilization reactive C x H y O z ‐containing intermediates bias product selectivity. In laboratory, chemists test hypotheses ideas, enabling rationalization why given metal/Lewis‐acid leads selective reduction outcomes. Concept identifies literature examples highlights key properties, allowing interested contributors design, create, implement novel productive transformations small molecule huge potential impact.

Language: Английский

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An Interactive Exploration of the Societal Impacts of Inorganic Chemistry─A Base Metal View on Sustainable Catalysis

Journal of Chemical Education, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 10, 2025

Language: Английский

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Ni-Catalyzed Cyanation of (Hetero)Aryl Electrophiles Using the Nontoxic Cyanating Reagent K₄[Fe(CN)₆]

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(8), P. 6459 - 6465

Published: April 5, 2025

A Ni-catalyzed cyanation of aryl halides using potassium ferrocyanide (K4[Fe(CN)6]) as a nontoxic cyanide source has been developed. Key features this method include the use biphasic aqueous conditions to overcome innate insolubility K4[Fe(CN)6] in organic solvents and bench-stable Ni(II) precatalyst combined with commercially available JosiPhos ligand that enhances practicality scalability reaction. The inclusion acidic additive tetrabutylammonium hydrogen sulfate was found improve reaction rate conversion. initial scope successfully demonstrated on range (hetero)aryl bromides, chlorides, sulfamates catalyst loadings low 2.5 mol %. This base-metal-catalyzed methodology further translated decagram synthesis pharmaceutical intermediate, usurping prior Pd-catalyzed process employed hazardous solvent pair (Zn(CN)2, DMAc).

Language: Английский

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Flash Communication: Oxidative Addition of 3-Iodopyridine at a Nickel Diphosphine Complex: Probing Secondary Borane Effects

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

Published: April 9, 2025

Language: Английский

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Broadly Applicable Copper(I)-Catalyzed Alkyne Semihydrogenation and Hydrogenation of α,β-Unsaturated Amides Enabled by Bifunctional Iminopyridine Ligands

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

A highly active bifunctional catalyst consisting of a copper(I)/N-heterocyclic carbene complex and basic 2-iminopyridine subunit allows for copper hydride chemistry under low H2 pressure, achieving efficient catalysis reaching 1 bar (balloon pressure). The tolerates remarkable variety functional groups in catalytic alkyne semihydrogenations. Furthermore, this design gives rise to high reactivity that the hydrogenation α,β-unsaturated amides (a substrate class hitherto unreactive catalysis) at pressure first time. In manner, late-stage modification isotope labeling amides, common subunits biologically compounds, can be realized through using first-row transition metal based on abundant copper. Preliminary mechanistic experiments indicate operates via an iminopyridine-mediated proximity effect. We hypothesize coordination alcohol as proton source copper(I) facilitates overall reactions rapid proto-decupration step.

Language: Английский

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Diversification of Pharmaceutical Manufacturing Processes: Taking the Plunge into the Non-PGM Catalyst Pool

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(13), P. 9708 - 9733

Published: June 13, 2024

Recent global events have led to the cost of platinum group metals (PGMs) reaching unprecedented heights. Many chemical companies are therefore starting seriously consider and evaluate if where they can substitute PGMs for non-PGMs in their catalytic processes. This review covers recent highly relevant applications non-PGM catalysts modern pharmaceutical industry. By highlighting these selected successful examples non-PGM-catalyzed processes from literature, we hope emphasize enormous potential catalysis inspire further development within this field enable technology progress toward manufacturing We also present some historical contexts perceived advantages challenges implementing environment.

Language: Английский

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Co(II)-Catalyzed Additive-Free Transfer Hydrogenation of N-Heteroarenes at Room Temperature

Organic Letters, Journal Year: 2024, Volume and Issue: 26(28), P. 6001 - 6005

Published: July 8, 2024

Traditional catalyst development relies on multistep synthesis and isolation of ligand precatalyst. Designing a catalytic system that can be assembled

Language: Английский

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Thermodynamic Modulation of Dihydrogen Activation Through Rational Ligand Design in Ge^II–Ni⁰ Complexes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 23606 - 23615

Published: Aug. 6, 2024

A family of chelating aryl-functionalized germylene ligands has been developed and employed in the synthesis their corresponding 16-electron Ni

Language: Английский

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Divergent Reactivity of a Cyclic Bis‐Hydridostannylene: A Masked Sn(I) Diradicaloid

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(21)

Published: Jan. 31, 2024

Herein, reactivity studies of a cyclic bis-hydridostannylene [(ADC)SnH]

Language: Английский

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Oxidatively-induced C(sp³)–C(sp³) bond formation at a tucked-in iron(iii) complex

Chemical Science, Journal Year: 2024, Volume and Issue: 15(27), P. 10359 - 10365

Published: Jan. 1, 2024

Carbon–carbon (C–C) bond formation is a cornerstone of synthetic chemistry, relying on routes such as transition-metal mediated cross-coupling for the introduction new carbon-based functionality.

Language: Английский

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