A Family of Cagelike Mn-Silsesquioxane/Bathophenanthroline Complexes: Synthesis, Structure, and Catalytic and Antifungal Activity

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(38), P. 15537 - 15549

Published: Sept. 12, 2023

This study reports a novel family of cage manganesesilsesquioxanes prepared via complexation with bathophenanthroline (4,7-diphenyl-1,10-phenanthroline). The resulting Mn4-, Mn6Li2-, and Mn4Na-compounds exhibit several unprecedented metallasilsesquioxane structural features, including intriguing self-assembly silsesquioxane ligands. Complexes were tested in vitro for fungicidal activity against seven classes phytopathogenic fungi. representative Mn4Na-complex acts as catalyst the cycloaddition CO2 to epoxides under solvent-free conditions form cyclic carbonates good yields.

Language: Английский

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Chalcogen Bonding in the Decoration of the Secondary Coordination Sphere of Copper(II) Complexes: Activation of Nitriles, the Auxiliary Ligand Substituent Effect

Crystal Growth & Design, Journal Year: 2023, Volume and Issue: 23(10), P. 7335 - 7344

Published: Aug. 30, 2023

The design of the secondary coordination sphere metal complexes has emerged as a powerful synthetic strategy in their application/function catalysis, molecular recognition, and crystal engineering. In contrast to traditional approaches, herein, copper(II) was designed by using chalcogen (sulfur) bond donor auxiliary ligands (5-substituted-1,3,4-thiadiazol-2-amines) one-pot activation one nitrile group an arylhydrazone ligand. ability markedly increases with electron-withdrawing character substituents, disclosed X-ray diffraction theoretical studies.

Language: Английский

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Computational Study on the Route of Cooperative Organocatalysis Utilizing Thiourea and Halogen Bond Donor Mixture

Russian Journal of General Chemistry, Journal Year: 2024, Volume and Issue: 94(S1), P. S129 - S137

Published: Jan. 1, 2024

Language: Английский

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Halogen Bonding in the Decoration of Secondary Coordination Sphere of Zinc(II) and Cadmium(II) Complexes: Catalytic Application in Cycloaddition Reaction of CO₂ with Epoxides

ACS Omega, Journal Year: 2023, Volume and Issue: 8(45), P. 42290 - 42300

Published: Nov. 1, 2023

Three new zinc(II) complexes [Zn(H2L3)2(H2O)3] (Zn2), [Zn(H3L2a)(H2O)3]n (Zn3) (H3L2a = 2,4-diiodo-5-(2-(2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)hydrazineyl)isophthalate) and [Zn(HL4)(DMF)(H2O)]n (Zn4) were synthesized by the reaction of Zn(II) salts with 5-(2-(2,4-dioxopentan-3-ylidene)hydrazineyl) isophthalic acid (H3L3), 2,4,6-triiodo-5-(2-(2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)hydrazineyl) (H5L2) (in presence NH2OH·HCl) 5-(2-(2,4-dioxopentan-3-ylidene)hydrazineyl)-2,4,6-triiodoisophthalic (H3L4), respectively. According to X-ray structural analysis, intramolecular resonance-assisted hydrogen bond ring remains intact, N···O distances 2.562(5) 2.573(5) Å in Zn2, 2.603(6) Zn3, 2.563(8) Zn4. In crystal packing cooperation I···O I···I types halogen bonds between tectons leads a one-dimensional supramolecular polymer, while interactions aggregate 1D chains coordination polymer These (Zn2, Zn4) known [Zn(H3L1)(H2O)2]n (Zn1) (H3L1 5-(2-(2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene) hydrazineyl)isophthalate), {[Zn(H3L1)(H2O)3]·3H2O}n (Zn5), [Cd(H3L1)(H2O)2]n (Cd1), {[Cd(HL3)(H2O)2(DMF)]·H2O}n (Cd2), [Cd(H3L3)]n (Cd-3), {[Cd2(μ-H2O)2(μ-H2L4)2(H2L4)2]·2H2O}n (Cd4), {[Cd(H3L1)(H2O)3]·4H2O}n (Cd5) tested as catalysts cycloaddition CO2 epoxides tetrabutylammonium halides cocatalyst. The halogen-bonded catalyst Zn4 is most efficient one bromide affording high yield (85-99%) cyclic carbonates under solvent-free conditions after 48 h at 40 bar 80 °C.

Language: Английский

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Understanding non-covalent interactions in Ni-catalyzed reactions: Mechanistic insights into stereoselective tetrasubstituted allene synthesis

Chem Catalysis, Journal Year: 2024, Volume and Issue: 4(9), P. 101082 - 101082

Published: Aug. 20, 2024

Language: Английский

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Stereoselective Entry into α,α’‐C‐Oxepane Scaffolds through a Chalcogen Bonding Catalyzed Strain‐Release C‐Septanosylation Strategy

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(29)

Published: April 30, 2024

Abstract The utility of unconventional noncovalent interactions (NCIs) such as chalcogen bonding has lately emerged a robust platform to access synthetically difficult glycosides stereoselectively. Herein, we disclose the versatility phosphonochalcogenide (PCH) catalyst facilitate into challenging, but biologically interesting 7‐membered ring α,α’‐ C ‐disubstituted oxepane core through an α‐selective strain‐release ‐glycosylation. Methodically, this strategy represents switch from more common entropically less desired macrocyclizations thermodynamically favored ring‐expansion approach. In light general lack stereoselective methods ‐septanosides, remarkable palette silyl‐based nucleophiles can be reliably employed in our method. This include broad variety useful synthons, easily available silyl‐allyl, silyl‐enol ether, silyl‐ketene acetal, vinylogous silyl‐alkyne and silylazide reagents. Mechanistic investigations suggest that mechanistic shift towards intramolecular aglycone transposition involving pentacoordinate silicon intermediate is likely responsible steering stereoselectivity.

Language: Английский

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Isomorphous Structures of Iron(II) Clathrochelates Featuring Terminal σ-Hole Donor Sites and Exhibiting the Cl/Br/I/S Quadruple Heteroisostructural Exchange

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(12), P. 4997 - 5006

Published: May 29, 2024

Upon crystallization from benzene–dichloromethane mixtures, the clathrochelates [Fe{FB[(–ON═C(Ph)C(Ph)═NO–)2(–ON═C(R)C(R)═NO–)]BF}] (R = Cl 1, Br 2, I 3; RR SCH2CH2S 4) release as isomorphous cocrystals (1–4)·2PhH, which were studied by X-ray diffractometry (XRD). In their XRD structures, short contacts of C–X···F–B attributed to a halogen bond (HaB; X Cl, Br, I) and chalcogen (ChB; S), both occurring in nearly same environment. This system presents unique case quadruple heteroisostructural exchange involving atoms different groups periodic table. These are involved two distinct types noncovalent interactions, namely, HaB ChB. The data used compare geometrical parameters computationally analyze nature σ-holes on sulfur found be directed way. result is relevant crystal engineering because it opens up route targeted design analogous supramolecular architectures via interchangeable

Language: Английский

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Photoelectrocatalytic System as a Reaction Platform for Selective Radical–Radical Coupling

Published: June 25, 2024

The selection of electrode material is a critical factor that determines the selectivity electrochemical organic reactions. However, fundamental principles governing this relationship are still largely unexplored. Herein, we demonstrate photoelectrocatalytic (PEC) system as promising reaction platform for selective radical–radical coupling owing to inherent charge-transfer properties photoelectrocatalysis. As model reaction, radical trifluoromethylation arenes shown on hematite photoanodes without employing molecular catalysts. PEC exhibited superior mono- bis-trifluoromethylated product compared conventional methods utilizing conducting anodes. Electrochemical and density functional theory (DFT) computational studies revealed controlling kinetics anodic oxidation aromatic substrates essential increasing selectivity. Only configuration could generate sufficiently high-energy charge carriers with controlled due generation photovoltage charge-carrier recombination, which characteristic features semiconductor photoelectrodes. This study opens novel approach towards reactions through understanding intrinsic physicochemical semiconducting materials.

Language: Английский

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A photoelectrocatalytic system as a reaction platform for selective radical–radical coupling

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Semiconducting photoanodes could generate high-energy charge carriers with controlled kinetics due to generation of photovoltage and recombination. The inherent charge-transfer properties enabled the efficient selective radical–radical coupling.

Language: Английский

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Heterolytic versus Homolytic: Theoretical Insight into the Ni⁰-Catalyzed Ph–F Bond Activation

Organometallics, Journal Year: 2023, Volume and Issue: 42(19), P. 2771 - 2783

Published: Sept. 14, 2023

The Ni0-catalyzed borylation of fluorobenzene (PhF) was theoretically investigated. Density functional theory (DFT) calculations disclosed that the Ph–F bond activation occurred heterolytically via an unprecedented nucleophilic aromatic substitution reaction (SNAr) assisted by sp2–sp3 diboron complex [B2nep2·(OPh)]-Na+, which forms a Ni0-ate as active species. diboron-ate stabilizes transition state through three interactions, Ni···O coordination, Na+···F cationic dipole interaction, and charge transfer arising from NaOPh. On other hand, catalyzed Ni0(dcpe) Ni0(PCy3)2 complexes has also been studied to allow comparison between monophosphine bisphosphine ligands. Results suggest is less effective than for concerted oxidative addition because Ni dπ orbital at lower energy level in equilibrium geometry. characteristic molecular features both (heterolytic) (homolytic) were disclosed.

Language: Английский

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