Enchanting Realm of Five-Membered Rare-Earth Metallacycles DOI
Wei Liu, Dajiang Huang, Junnian Wei

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: May 5, 2025

ConspectusMetallacycles, derivatives of carbocyclic compounds wherein a metal atom replaces at least one carbon center, have been constant powerhouse in organic synthesis. While metallacycles main-group, transition, and actinide metals extensively studied, those incorporating rare-earth (RE) elements (Sc, Y, lanthanides) remained elusive primarily due to synthetic challenges. Nevertheless, the electropositive character these resulting polarization RE-C bonds, along with intrinsic synergistic effects within metallacycles, endow RE unique properties rich, yet largely untapped, reaction chemistry. In this Account, we present development applications five-membered metallacycles.Over past decade, successfully synthesized variety all-carbon using two key strategies: (i) transmetalation, which has employed prepare metallacyclopentadienes spiro-metallacyclopentadienes, which, featuring various ligand systems, provide distinct coordination environments around significantly influencing their reactivity, (ii) transmetalation reduction, enabling synthesis spiro-metallacyclopentenes 2-butene tetraanion (BTA)-bridged dinuclear metallacyclopentenes. The reduction process proceeds via either self-disproportionation or by divalent centers alkali metals. These represent first instances such RE-containing metallacyclic ring structures.Our investigations into uncovered reactivities new modes. high reactivity multiple reactive sites enable them not only activate small molecules efficiently but also exhibit activation modes for some molecules. For instance, reactions carbodiimides showcase diverse insertion/rearrangement chemistry, influenced factors as number equivalents carbodiimide solvent choice. metallacyclopentadiene-mediated [3 + 1] fragmentation white phosphorus demonstrates an mode markedly different from that observed main-group transition analogs. Moreover, discovery cross-carbanion coupling RE-metal-mediated ring-opening metathesis benzene introduces modes, demonstrating that, rational design, can similar even surpassing further led chemistry.Additionally, novel uncovered, stemming geometric electronic structures. Structural analysis theoretical calculations revealed nonplanar aromaticity BTA-bridged metallacyclopentenes, extending concept chemistry carbon-RE metallacycles. Furthermore, benefiting redox capabilities butadiene dianion BTA ligands, ligand-based metallacyclopentenes efficient multielectron transfer processes, highlighting potential chemistry.The studies encompassing construction, characterization, properties, applications, greatly enriched field f-block We hope Account will inspire exploration organometallic reagents metallacycle-mediated transformations, fueling continued progress

Language: Английский

Redox Studies of the Scandium Metallocene (C5H2tBu3)2ScII Lead to a Terminal Side-On (N═N)2– Complex: [(C5H2tBu3)2ScIII(η2-N2)]− DOI
Joshua D. Queen, Ahmadreza Rajabi, Joseph W. Ziller

et al.

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

Published: March 31, 2025

Cyclic voltammetry measurements on the scandium(II) metallocene, Cpttt2ScII (Cpttt = C5H2tBu3), reveal a -1.87 V vs Fc+/Fc event assigned to [Cpttt2Sc]+/0 redox couple and -3.09 process [Cpttt2Sc]0/- couple, which are consistent with subsequent chemical studies. Chemical oxidation of AgBPh4 gives scandocenium cation salt [Cpttt2ScIII][BPh4], 1. The [Cpttt2ScIII]+ does not coordinate [BPh4]- anion or THF solvent; however, one methyl groups tert-butyl substituent has close interaction Sc(III) ion. Decomposition occurs in presence [nBu4N][PF6] supporting electrolyte, studies indicate that 1 reacts [PF6]- by fluoride abstraction form Cpttt2ScIIIF PF5. reduction proceeds Cp*2SmII Cp*2CoII (Cp* C5Me5), is measured potentials. was observed react N2; treatment KC8 18-crown-6 (crown) under N2 forms (N═N)2- complex, Cpttt2ScIII(μ-η2:η2-N2)K(crown), 2. reaction 2.2.2-cryptand (crypt) generates [K(crypt)][Cpttt2ScIII(η2-N2)], 3, first isolable complex any metal terminal side-on ligand. These LnIIA2/M/N2 reactions (M alkali metal; (A)- anion) Ln(II)/Ln(I) analogs previously reported Ln(III)/Ln(II) reactions, LnIIIA3/M/N2, Ln(III) complexes Ln(II) reactivity complexes.

Language: Английский

Citations

0
Monomeric M(II) (M = Fe, Co, Ni) complexes supported by bulky aryloxide ligands tethered to an arene functionality; synthesis, electrochemistry and study of the M(II)-arene interaction. DOI Creative Commons

Ioannis Vagiakos,

Nikolaos Tsoureas,

Tianyin Huang

et al.

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Strength of M–arene interaction (2-Ni) ≫ (2-Co) > (2-Fe), IR spectroscopy to probe interaction, THF coordination completely disturbs interaction.

Language: Английский

Citations

0
Visible-Light Photocatalytic Degradation of Methylene Blue by Yb3+-Doped 3D Nanosheet Arrays BiOI Anchored on High-Chloride Fly Ash Composites DOI Creative Commons

Shuxian Qiu,

Danhua Zhao,

Rong Luo

et al.

Inorganics, Journal Year: 2025, Volume and Issue: 13(5), P. 147 - 147

Published: May 6, 2025

A Yb3+-doped BiOI 3D nanosheet array composite was successfully fabricated through a solvothermal deposition strategy on flexible carbon cloth (CC). This subsequently integrated with high-chlorine fly ash (FA) blocks to form the Yb-BiOI/CC/FA hybrid material. Comprehensive characterization performed using multiple analytical techniques for crystalline phase identification, morphological analysis, valence state, band structure evaluation, and charge carrier separation assessment. Electrochemical measurements were conducted evaluate material’s electronic properties. Experimental results demonstrated superior photocatalytic performance under visible light irradiation, achieving 52.87% methylene blue degradation efficiency. The reaction rate constant of this modified nanomaterial approximately 2.1 times higher than that pristine BiOI/CC/FA. Radical trapping experiments revealed superoxide radicals (·O2−) served as predominant oxidative species. study presents dual-benefit environmental remediation by simultaneously sustainable waste valorization industrial byproducts developing high-efficiency materials. successful integration rare-earth metal modification substrate engineering provides valuable insights designing advanced systems pollutant degradation.

Language: Английский

Citations

0
Enchanting Realm of Five-Membered Rare-Earth Metallacycles DOI
Wei Liu, Dajiang Huang, Junnian Wei

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: May 5, 2025

ConspectusMetallacycles, derivatives of carbocyclic compounds wherein a metal atom replaces at least one carbon center, have been constant powerhouse in organic synthesis. While metallacycles main-group, transition, and actinide metals extensively studied, those incorporating rare-earth (RE) elements (Sc, Y, lanthanides) remained elusive primarily due to synthetic challenges. Nevertheless, the electropositive character these resulting polarization RE-C bonds, along with intrinsic synergistic effects within metallacycles, endow RE unique properties rich, yet largely untapped, reaction chemistry. In this Account, we present development applications five-membered metallacycles.Over past decade, successfully synthesized variety all-carbon using two key strategies: (i) transmetalation, which has employed prepare metallacyclopentadienes spiro-metallacyclopentadienes, which, featuring various ligand systems, provide distinct coordination environments around significantly influencing their reactivity, (ii) transmetalation reduction, enabling synthesis spiro-metallacyclopentenes 2-butene tetraanion (BTA)-bridged dinuclear metallacyclopentenes. The reduction process proceeds via either self-disproportionation or by divalent centers alkali metals. These represent first instances such RE-containing metallacyclic ring structures.Our investigations into uncovered reactivities new modes. high reactivity multiple reactive sites enable them not only activate small molecules efficiently but also exhibit activation modes for some molecules. For instance, reactions carbodiimides showcase diverse insertion/rearrangement chemistry, influenced factors as number equivalents carbodiimide solvent choice. metallacyclopentadiene-mediated [3 + 1] fragmentation white phosphorus demonstrates an mode markedly different from that observed main-group transition analogs. Moreover, discovery cross-carbanion coupling RE-metal-mediated ring-opening metathesis benzene introduces modes, demonstrating that, rational design, can similar even surpassing further led chemistry.Additionally, novel uncovered, stemming geometric electronic structures. Structural analysis theoretical calculations revealed nonplanar aromaticity BTA-bridged metallacyclopentenes, extending concept chemistry carbon-RE metallacycles. Furthermore, benefiting redox capabilities butadiene dianion BTA ligands, ligand-based metallacyclopentenes efficient multielectron transfer processes, highlighting potential chemistry.The studies encompassing construction, characterization, properties, applications, greatly enriched field f-block We hope Account will inspire exploration organometallic reagents metallacycle-mediated transformations, fueling continued progress

Language: Английский

Citations

0