Reply to: On the existence of collective interactions reinforcing the metal-ligand bond in organometallic compounds

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: July 3, 2023

Language: Английский

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Pd-catalysed hydrodehalogenation of aryl chlorides: a mild method for deuteration and detoxification

Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(12), P. 3545 - 3550

Published: Jan. 1, 2023

The hydrodehalogenation of haloarenes at room temperature using ethanol as hydride source and a Pd-catalyst with an ylide-substituted phosphine is reported. protocol can be used for deuterations detoxifications chlorinated biphenyls.

Language: Английский

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P,N‐Coordinating Ylide‐Functionalized Phosphines (NYPhos): A Ligand Platform for the Selective Monoarylation of Small Nucleophiles

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 20, 2024

Palladium-catalyzed coupling reactions of small nucleophiles are great interest, but challenging due to difficulties in selectivity control. Herein, we report the development a new platform P,N-ligands consisting ylide-functionalized phosphines with aminophosphonium groups (NYPhos) address this challenge. These phosphine ligands easily accessible wide structural diversity highly modular electronic and steric properties. Based on family 14 selective monoarylation acetone as well other ketones amides was accomplished record-setting activities even for aryl chlorides at room temperature including late-stage functionalizations drug molecules. Moreover, ammonia primary amines could be coupled mild conditions. Isolation structure analyses palladium complexes within catalytic cycle confirmed that P,N-coordination mode is necessary achieve observed selectivities. It also demonstrated facile adjustability N-donor strength, which beneficial targeted design tailored future applications.

Language: Английский

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Palladium-Catalyzed Coupling of Aryl Chlorides with Secondary Phosphines to Construct Unsymmetrical Tertiary Phosphines

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 29, 2024

The functionalization of the C-Cl bond in unactivated aryl chlorides under mild conditions presents a significant challenge. We disclose general protocol for constructing both partially and entirely unsymmetrical tertiary phosphines through Pd/keYPhos-catalyzed coupling with secondary conditions. reaction exhibits excellent functional group tolerance broad substrate scopes. Furthermore, rapid synthesis ligands luminescent compound sTPPs, alongside gram-scale systhesis, demonstrates practical applicability this method.

Language: Английский

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Stabilisation and reactivity studies of donor-base ligand-supported gallium-phosphides with stronger binding energy: a theoretical approach

RSC Advances, Journal Year: 2023, Volume and Issue: 13(12), P. 7738 - 7751

Published: Jan. 1, 2023

Gallium phosphide is a three-dimensional polymeric material of the hetero-diatomic GaP unit, which has wurtzite type structure, and captivating application as light emitting diode (LED). As result, there constant search for suitable precursors to synthesise GaP-based materials. However, corresponding monomeric species exotic in nature due expected Ga[triple bond, length m-dash]P multiple bond. Herein, we report on theoretical studies stability, chemical bonding, reactivity gallium phosphides with two donor base ligands having tuneable binding energies. We have performed detailed investigations using density functional theory at three different levels (BP86/def2-TZVPP, B3LYP/def2-TZVPP, M06-2X/def2-TZVPP), QTAIM EDA-NOCV (BP86-D3(BJ)/TZ2P, M06-2X/TZ2P) analyse various ligand-stabilised monomers, revealed synthetic viability such presence stable singlet carbenes, e.g., cAAC, NHC [cAAC = cyclic alkyl(amino) carbene, N-heterocyclic carbene] larger bond dissociation energy compared phosphine ligand (PMe3). The calculated energies between pair unit are found be range 87 137 kcal mol-1, predicting their possible syntheses laboratory. Further, metal carbonyls [Fe(CO)4, Ni(CO)3] been theoretically investigated.

Language: Английский

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Carbanion-functionalized phosphines: New design elements for catalyst development

Advances in catalysis, Journal Year: 2023, Volume and Issue: unknown, P. 1 - 56

Published: Jan. 1, 2023

Language: Английский

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P,N‐koordinierende Ylid‐funktionalisierte Phosphane (NYPhos): Eine Ligandenplattform für die selektive Monoarylierung kleiner Nukleophile

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(36)

Published: June 20, 2024

Abstract Palladium‐katalysierte Kupplungsreaktionen von kleinen Nukleophilen sind großem Interesse, aber aufgrund der schwierigen Selektivitätskontrolle eine synthetische Herausforderung. Wir berichten nun über die Entwicklung einer neuen Plattform an P,N ‐Liganden bestehend aus Ylid‐funktionalisierten Phosphanen mit Aminophosphoniumgruppen (NYPhos), um dieses Problem zu lösen. Die Phosphanliganden in großen strukturellen Breite leicht zugänglich, wodurch ihre elektronischen und sterischen Eigenschaften flexibel variiert werden können. Basierend auf Serie 14 NYPhos‐Liganden konnte selektive Monoarylierung Aceton anderer anspruchsvoller Ketone Amide rekordverdächtigen Aktivitäten auch für Arylchloride bei Raumtemperatur erreicht werden, einschließlich Funktionalisierung Wirkstoffmolekülen. Darüber hinaus konnten Ammoniak andere kleine primäre Amine unter milden Bedingungen gekoppelt werden. Isolierung Strukturanalyse Palladiumkomplexen innerhalb des katalytischen Zyklus bestätigte den ‐Koordinationsmodus Liganden, zur Erzielung beobachteten Selektivitäten erforderlich ist. Zudem erwies sich Stärke N‐Donors als einstellbar, was das gezielte Design maßgeschneiderter künftige Anwendungen Vorteil sein sollte.

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Influence of Ylide Functionalization on the Catalytic Performance of Ferrocenyldiphosphines in Au(I)‐Catalyzed Hydroaminations and Hydrohydrazinations

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(16)

Published: April 10, 2024

Abstract Ylide‐functionalized phosphines (YPhos) have been shown to yield highly active gold catalysts owing their high donor capacity. To examine the impact of ylide functionalization on a given ligand structure, series ferrocenyl diphosphines functionalized with no, one or two moieties and corresponding bimetallic complexes were prepared. The feature an anti‐conformation phosphine moieties, guaranteeing presence independent metal centers. Comparative studies in hydroamination hydrohydrazination alkynes revealed significant increase catalytic activity for each newly introduced group. di‐YPhos ligands be most precatalysts, functioning effectively even at 0.1 0.2 mol % catalyst loading. This efficiency was demonstrated alkynes, amines hydrazines.

Language: Английский

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Palladium-catalyzed N-arylation of (hetero)aryl chlorides with pyrroles and their analogues

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 26, 2024

A practical method for N -arylation of N–H heteroarenes with aryl chlorides through Pd/keYPhos catalyzed selective cleavage the Ar–Cl bond under mild conditions has been developed.

Language: Английский

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