Divergent Reactivity of <i>E</i>/<i>Z</i>‐Azobenzene‐Based Phosphine‐Gold Catalysts: Toward an ON‐ON Catalytic Photoswitch Process DOI Creative Commons

Nawel Goual,

Stéphane Maisonneuve, Fabrizio Medici

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 367(1)

Published: Oct. 17, 2024

Abstract This work discloses a strategy for the implementation of ON‐ON organometallic catalytic processes using photoresponsive phosphine ligands. The approach leverages on regiodivergent reactivity mono‐ and bimetallic gold complexes that results from π‐ vs σ,π‐activations alkynyl‐substituted urea substrates, selective formation either dihydroquinazolinone or indole‐carboxamide products, via intramolecular hydroamidation.

Language: Английский

Mechanistic Insights into Molecular Copper Hydride Catalysis: the Kinetic Stability of CuH Monomers toward Aggregation is a Critical Parameter for Catalyst Performance DOI
David E. Ryan, Jack T. Fuller, Evan A. Patrick

et al.

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

Published: March 31, 2025

The activity of molecular copper hydride (CuH) complexes toward the selective insertion unsaturated hydrocarbons under mild conditions has contributed significantly to versatile methodologies for upgrading these feedstocks. However, catalysts are particularly susceptible deleterious aggregation, leading depletion active CuH species. Little is known about mechanisms how it influences overall catalyst performance, and can be controlled. We address challenges with mechanistic studies on a model reaction unactivated alkene hydroboration catalyzed by (IPr*CPh3)CuH (LCuH). report comprehensive investigation this system, identifying an aggregation pathway that continuously depletes catalytically LCuH form inactive clusters during turnover. Deactivation controlled primarily competition between kinetics initial dimerization step into LCuH. therefore propose understanding performance must account step, revising previously explored thermodynamic where concentration species equilibria established monomers. With series (NHC)CuH congeners (NHC = N-heterocyclic carbene), we demonstrate ostensibly minor structural modifications ligand peripheries drastically affect kinetics, while maintaining reactivity on-cycle insertion. employed computational approach based dynamics simulations provide in-depth specific substantially increase kinetic stability monomeric catalysts. Our combined experimental suggest strategies rational design broadly applied systems deactivation via pathways.

Language: Английский

Citations

1
Recoverable and Sensitive Pressure-Induced Mechanochromic Photoluminescence of a Au-P Complex DOI Creative Commons

Ningwen Yang,

Y. C. Chang,

Jiangyue Wang

et al.

Molecules, Journal Year: 2025, Volume and Issue: 30(9), P. 2011 - 2011

Published: April 30, 2025

A binuclear Au-P complex [Au2(2-bdppmapy)2](PF6)2 (1) was synthesised by the reaction of 2-bdppmapy (N,N′-bis-(diphenylphosphanylmethyl-2-aminopyridine) with AuCN and [Cu(MeCN)4]PF6. The solid phase 1 emitted bright yellow phosphorescence at λmax = 580 nm under UV excitation (QY 4.41%, τ 1.88 μs), which shifted to green (λmax 551 nm, QY 5.73%) after being pressurised 5 MPa. This colour change recoverable upon exposure CH2Cl2 vapor. Similar mechanochromic photoluminescence behaviour observed grinding crystals 1. filter paper impregnated demonstrated recyclable write/erase functionality for encrypted information transfer.

Language: Английский

Citations

0
Photoredox-mediated cobalt catalysis for non-asymmetric and asymmetric synthesis DOI Creative Commons

Zhiyong Chi,

Yuhang He,

Ablimit Abdukader

et al.

Cell Reports Physical Science, Journal Year: 2025, Volume and Issue: unknown, P. 102613 - 102613

Published: May 1, 2025

Language: Английский

Citations

0
77Se NMR spectroscopy of selenium adducts of N-heterocyclic carbenes DOI

Sean Ray Kahnert,

Lucas Pruschinski,

Andreas Schmidt

et al.

Advances in heterocyclic chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Language: Английский

Citations

2
Synthesis and DFT Investigations of Novel 13-(Pyrimidin-2-yl)-6H,12H-6,12-Epiminodibenzo[b,f][1,5]dioxocine Derivatives DOI

Ruo-Xin Li,

Yan Zhang, Peng-Wei Chen

et al.

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: unknown, P. 140398 - 140398

Published: Oct. 1, 2024

Language: Английский

Citations

1
Supramolecular systems and their connection with metal–organic structures DOI Creative Commons
Rodrigo Cué-Sampedro, José Antonio Sánchez-Fernández

Frontiers in Chemistry, Journal Year: 2024, Volume and Issue: 12

Published: Nov. 5, 2024

Supramolecular structures with specific applications are a pillar in several areas of science. Thus, from contemporary point view, there reasons to embrace systematic order the supramolecular concept itself. First, structuring material seems safer now than it did decades ago. Second, interactions metal–organic frameworks (MOFs) and chemistry and, conversely, supramolecularity assemble MOFs create efficient complex systems multiple cutting-edge an image be safeguarded. Third, perhaps we should simply limit ourselves considering how researchers these fields have attempted correlate notion by linking self-assembly considerations. In any case, topics present advantages optimize innovative geometries that useful highlight significant practical applications. This review covers general introduction supramolecularity, key unit study presented here, followed survey recent advances confined space chemistry, relationships structures, synthesis electrochemistry switchable obtain greater understanding structure–property relationships. To conclude, some future perspectives on this promising plausible field science will mentioned.

Language: Английский

Citations

1
No Switching Cooperativity between Coordinated Azo Ligands on Complexes Having {MII(phosphane-κ2P)}2+ (M = Pd, Pt) Scaffolds DOI Creative Commons

Ot Raïch Panisello,

Jesús Jover, Cristina Puigjaner

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(35), P. 16251 - 16263

Published: Aug. 21, 2024

A series of square-planar palladium and platinum compounds with cis-blocking phosphanes terminal azobenzene ligands [M(dppp)(azo)2](OTf)2 (azo = CN(C6H4)-N═N-(C6H4)CN (iso-cyano), CN(C6H4)-N═N-(C6H5) (iso-Ph)) [{M2(tpbz)}(azo)4](OTf)4 have been synthesized fully characterized. Similarly to the uncoordinated ligands, new coordination shown be photochemically active respect their trans-to-cis isomerization process. Their cis-to-trans back spontaneous reaction studied as a function solvent, temperature pressure corresponding activation parameters determined in order investigate mechanism these transformations. The results obtained are indicative operation rotational no cooperativity between azo attached same metal. Density functional theory calculations carried out estimate relative energies different photoisomers for theoretical interpretation experimental data.

Language: Английский

Citations

0
Divergent Reactivity of <i>E</i>/<i>Z</i>‐Azobenzene‐Based Phosphine‐Gold Catalysts: Toward an ON‐ON Catalytic Photoswitch Process DOI Creative Commons

Nawel Goual,

Stéphane Maisonneuve, Fabrizio Medici

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 367(1)

Published: Oct. 17, 2024

Abstract This work discloses a strategy for the implementation of ON‐ON organometallic catalytic processes using photoresponsive phosphine ligands. The approach leverages on regiodivergent reactivity mono‐ and bimetallic gold complexes that results from π‐ vs σ,π‐activations alkynyl‐substituted urea substrates, selective formation either dihydroquinazolinone or indole‐carboxamide products, via intramolecular hydroamidation.

Language: Английский

Citations

0