Sterically Induced Acceleration of Aryl Halide Activation by Pd(0): A Radical Alternative to 2-Electron Oxidative Addition DOI

Daniel Hupperich,

Jaime Ponce‐de‐León, Ignacio Funes‐Ardoiz

et al.

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

Published: May 29, 2025

The first elementary step of Pd(0)-catalyzed cross-coupling involves the activation an aryl halide by a Pd(0) catalyst, which is widely assumed to proceed in formal 2-electron process, involving concerted cleavage bond and formation aryl-Pd as generate Pd(II) complex. Contrary common reactivity assumptions under this mechanistic manifold, we observed that severe steric hindrance catalyst did not inhibit thermal but instead greatly accelerated it, giving full conversion ortho,ortho-di-tert-butyl-substituted bromide 1 min at room temperature on gram scale with bulky catalyst. Our data revealed 1-electron-based halogen abstraction operative such sterically demanding settings.

Language: Английский

Molecular Design Principles for Photoactive Transition Metal Complexes: A Guide for “Photo-Motivated” Chemists DOI Creative Commons
Giacomo Morselli, Christian Reber, Oliver S. Wenger

et al.

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

Published: March 27, 2025

Luminescence and photochemistry involve electronically excited states that are inherently unstable therefore spontaneously decay to electronic ground states, in most cases by nonradiative energy release generates heat. This dissipation can occur on a time scale of 100 fs (∼10–13 s) usually needs be slowed down at least the nanosecond (∼10–9 for luminescence intermolecular occur. is challenging task with many different factors consider. An alternative emerging strategy target dissociative lead metal–ligand bond homolysis subnanosecond access synthetically useful radicals. Based thorough review recent advances field, this article aims provide concise guide obtaining luminescent photochemically coordination compounds d-block elements. We hope encourage "photo-motivated" chemists who have been reluctant apply their synthetic other knowledge photophysics photochemistry, we intend stimulate new approaches control state behavior.

Language: Английский

Citations

0

Fine-Tuning the Excited-State Dynamics of Heteroleptic Ruthenium(II) Polypyridyl Complexes with Systematic Variation of Benzazole-Substituted 8-Hydroxyquinolines DOI
Abhijit Saha, Subhas C. Kundu, Mahendra K. Verma

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 30, 2025

A series of structurally related bistridentate heteroleptic Ru(II) polypyridyl complexes, [RuII(ttpy)(8-HQLS/N/O)]+ (Ru1-Ru3), were synthesized, where ttpy = p-tolyl terpyridine and 8-HQLS/N/O are monoanionic N^N^O-donor tridentate ligands (8-HQLX), derived from 8-hydroxyquinoline (8-HQ), namely, 8-HQLS 2-(2'-benzothiazole)-8-hydroxyquinoline, 8-HQLN 2-(2'-benzimidazole)-8-hydroxyquinoline, 8-HQLO 2-(2'-benzoxazole)-8-hydroxyquinoline. The electronic structures these rigid systematically tuned by varying the noncoordinating heteroatoms (S, O, NH) in five-membered heterocyclic ring, impacting properties, redox potentials, excited-state lifetime/dynamics, deactivation pathways photophysical behavior corresponding complexes. Notably, [RuII(ttpy)(8HQLN)]+ (Ru2) exhibited an lifetime (τ > 1 ns CH3CN at RT) surpassing that homoleptic complex [Ru(ttpy)2]2+ ∼ 0.62 ns), despite its more distorted octahedral geometry. These complexes (Ru1-Ru3) showed extended lifetimes compared to their counterpart Ru4. displayed absorption red region, which is favorable for phototherapeutic applications. Their relative singlet oxygen (1O2) quantum yields (ΦΔ) ranged 0.03 0.10. Given reasonable 1O2 generation ability, demonstrated potential as photocatalysts organic substrates, evidenced effectiveness photooxidation PPh3 Ph3P=O a model reaction.

Language: Английский

Citations

0

Wearable devices for monitoring sweat glucose: an integrated strategy for efficient electrochemical sensors DOI Creative Commons
Ruiyu Luo, Yi Yang, Senlin Huang

et al.

Sensors and Actuators Reports, Journal Year: 2025, Volume and Issue: 9, P. 100339 - 100339

Published: May 21, 2025

Language: Английский

Citations

0

Sterically Induced Acceleration of Aryl Halide Activation by Pd(0): A Radical Alternative to 2-Electron Oxidative Addition DOI

Daniel Hupperich,

Jaime Ponce‐de‐León, Ignacio Funes‐Ardoiz

et al.

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

Published: May 29, 2025

The first elementary step of Pd(0)-catalyzed cross-coupling involves the activation an aryl halide by a Pd(0) catalyst, which is widely assumed to proceed in formal 2-electron process, involving concerted cleavage bond and formation aryl-Pd as generate Pd(II) complex. Contrary common reactivity assumptions under this mechanistic manifold, we observed that severe steric hindrance catalyst did not inhibit thermal but instead greatly accelerated it, giving full conversion ortho,ortho-di-tert-butyl-substituted bromide 1 min at room temperature on gram scale with bulky catalyst. Our data revealed 1-electron-based halogen abstraction operative such sterically demanding settings.

Language: Английский

Citations

0