Electrochemically Gated Frustrated Lewis Pair Chemistry in Electric Double Layer DOI
Hang Guo, Qiang Wan,

Yunjia Jiang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 8, 2024

Abstract The recent discovery of frustrated Lewis pairs (FLPs) during the activation small molecules has inspired extensive research across full span chemical science. Owing to nature weak interactions, it is experimentally challenging directly observe and modulate FLP at molecular scale. Here we design a boron cluster anion building block (B 10 H 8 2− ) organic amine cations ([NR 4 ] + , R=−CH 3 −C 2 5 as prove feasibility controlling their interaction in electric double layer (EDL) via an electrochemical strategy. In situ single‐molecule electrical measurements Raman monitoring B −[NR formed positively charged Au(111) electrode surface, contrast free‐standing near or below potential zero charge (PZC). Furthermore, this chemistry leads shift local density states clusters towards E F for enhancing electron transport, providing new prototype reversible single‐cluster switch that digitally switches upon layer.

Language: Английский

Cooperative Heterobimetallic CO2 Activation Involving a Mononuclear Aluminum(II) Intermediate DOI
Roushan Prakash Singh, Kevin P. Quirion, Joshua Telser

et al.

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

Published: April 3, 2025

Molecular chemistry of aluminum most commonly involves AlIII ions due to their noble gas electronic configurations. In contrast, the AlII is underexplored and may contain undiscovered reaction manifolds. Here, we report CO2 activation a transient intermediate supported by chelating, dianionic ligand investigate structure details mechanisms required access this reactivity. We found that heterobinuclear complex, (NON)Al-FeCp(CO)2 (1), undergoes Al-Fe bond homolysis at ambient conditions reveal [(NON)Al]•/[CpFe(CO)2]• radical pair in situ. The presence predominantly Al-centered spin density (i.e., an ion) within was established quantum-chemical calculations with experiments which scavengers (TEMPO, benzophenone) induce homolysis. Exposure 1 atmosphere resulted insertion into bond. This net 2-electron reduction process computationally modeled using functional theory direct dynamics simulations, revealing two 1-electron steps and, thus, depends on stabilization high-energy [CO2]•- coordination aluminum. mechanism for unexpected given canonical predisposition multielectron processes demonstrates possibility discovering new profiles earth-abundant elements unusual oxidation states.

Language: Английский

Citations

0
Structural Snapshots of Reversible Carbon Dioxide Capture and (De)oxygenation at Group 14 Diradicaloids DOI
Falk Ebeler,

Beate Neumann,

Hans‐Georg Stammler

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 8, 2024

Although diradicals should exhibit a rather small reaction barrier as compared to closed-shell species for activating kinetically inert molecules, the activation and functionalization of carbon dioxide with stable main-group remain virtually unexplored. In this work, we present thorough study on CO2 activation, reversible capture, (de)oxygenation mediated by Group 14 singlet (i.e., diradicaloids) [(ADC)E]2 (E = Si, Ge, Sn) based an anionic dicarbene (ADC) framework (ADC PhC{N(Dipp)C}2; Dipp 2,6-iPr2C6H3). readily undergo [4 + 2]-cycloadditions result in barrelene-type bis-metallylenes [(ADC)E]2(OC═O). The addition is E Ge; thus, detaches under vacuum or at elevated temperature regenerates [(ADC)Ge]2. [(ADC)Sn]2(OC═O) isolable but deoxygenates additional form [(ADC)Sn]2(O2CO) CO. [(ADC)Si]2(OC═O) extremely reactive could not be isolated detected it spontaneously reacts further yield elusive monomeric Si(IV) oxides [(ADC)Si(O)]2(COn) carbonates [(ADC)Si(CO3)]2(COn) (n 1 2) via CO2. molecular structures all compounds have been established X-ray diffraction, mechanistic insight their formation has suggested DFT calculations.

Language: Английский

Citations

3
Anionic or Radical Polymerization Catalyzed by Metal Triflate-Based Lewis Pairs: A Comprehensive Mechanistic Study DOI

Riki Akita,

Mayo Horibe,

Katsuhiro Yamamoto

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(10), P. 4926 - 4936

Published: May 15, 2024

Ester and amide enolates are important propagating species in organometallic-mediated polymerization of polar vinyl monomers, but the effects transition main group metallic counterions have not been systematically understood. In this study, various metal triflates along with PPh3 used to catalyze Lewis pair anionic (LPAP) or radical (LPRP) (meth)acrylates acrylamides, elements solvents determine dominant propagation mechanism. Specifically, LPAP LPRP proceed using early late triflates, respectively, organic on-water. The elementary reactions PPh3/Fe(OTf)3 kinetically investigated. Notably, follows pseudo-second-order kinetics respect monomer concentration, which contributes initiation propagation, whereas PPh3/Sc(OTf)3 proceeds pseudo-zero-order kinetics. This indicates that react unactivated free Sc-activated LPAP. study demonstrates triflate-based pairs can generate new polymerizable distinctive reactivities.

Language: Английский

Citations

2
p-Diarylboryl Halothiophenols as Multifunctional Catalysts via Photoactive Intramolecular Frustrated Lewis Pairs DOI

Takeru Kikura,

Y. B. Taura,

Yoshitaka Aramaki

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 20425 - 20431

Published: July 8, 2024

p-Diarylboryl halothiophenols are developed and unequivocally characterized. Their photophysical properties catalytic performance unveiled by experimental theoretical investigations. This novel class of triarylboranes behaves as a Brønsted acid to generate the corresponding borylthiophenolate that can absorb visible light undergo intramolecular charge transfer form radical pair consisting boron anion thiyl radical, which acts single-electron reductant while engaging in hydrogen atom regenerate parent borylthiophenol. The synthetic relevance this mode action is demonstrated establishment unique catalysis integrates three different yet tunable functions single cycle, thereby allowing borylthiophenols solely promote assembly sterically congested 1,2-diols 1,2-aminoalcohol derivatives via radical–radical cross-coupling.

Language: Английский

Citations

2
Lessons from recent theoretical treatments of Al-M bonds (M = Fe, Cu, Ag, Au) that capture CO2 DOI
S. M. Supundrika Subasinghe, Neal P. Mankad

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(33), P. 13709 - 13715

Published: Jan. 1, 2024

Complexes with Al-M bonds (M = transition metal) have emerged as platforms for discovering new reaction chemistry either through cooperative bond activation behaviour of the heterobinuclear unit or by modifying properties M site its interaction Al centre. Therefore, elucidating nature bonding is critical to advancing this research area and typically involves careful theoretical modelling. This Frontier article reviews selected recent case studies that included treatments bonds, specifically highlighting complexes capable CO

Language: Английский

Citations

2
Synthesis and Photochemical Uncaging of Alkene-Protected, Polymer-Bound Vicinal Frustrated Lewis Pairs DOI Creative Commons
Emily A. Latif, Jeremy D. Hilgar, Nathan A. Romero

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(36), P. 24764 - 24769

Published: Aug. 26, 2024

Polymeric materials bearing Frustrated Lewis Pair (FLP) functionality are promising candidates for use as heterogeneous catalysts and adaptive materials, but synthetic access to FLP-functional polymers remains limited due the incompatibility of FLPs with standard polymerization chemistries. Herein, we describe a approach that "cages" highly reactive vicinal phosphine-borane covalent alkene adducts, which stable Ni-mediated vinyl addition polymerization. We discovered caged FLP adducts can be photochemically activated liberate FLPs, enabling spatiotemporally controlled release from polymeric precursors.

Language: Английский

Citations

2
Light-Induced Polymeric Frustrated Radical Pairs as Building Blocks for Materials and Photocatalysts DOI Creative Commons
Meng Wang, Muralidharan Shanmugam, Eric J. L. McInnes

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(44), P. 24294 - 24301

Published: Oct. 27, 2023

Polymeric frustrated Lewis pairs, or poly(FLP)s, have served to bridge the gap between functional polymer science and main group catalysis, pairing uniqueness of sterically acids bases with a scaffold create self-healing gels recyclable catalysts. However, their utilization in radical chemistry is unprecedented. In this paper, we disclose synthesis polymeric poly(FRP)s, by situ photoinduction FLP moieties, where acidic basic centers are tuned promote single electron transfer (SET). Through systematic manipulation chemical structure, demonstrate that inclusion ortho-methyl groups on phosphine monomers crucial enable SET. The generation radicals evidenced monitoring stable cations via UV/vis EPR spectroscopy. These new poly(FRP)s both catalytic hydrogenation radical-mediated photocatalytic perfluoroalkylations. systems open avenues design novel polymers for catalysis photoelectrical chemistry.

Language: Английский

Citations

6
Sequential radical and cationic reactivity at separated sites within one molecule in solution DOI Creative Commons
Zhongshu Li, Yinwu Li,

Jieli Lin

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(14), P. 5376 - 5384

Published: Jan. 1, 2024

Distonic radical cations (DRCs) with spatially separated charge and sites are expected to show both cationic reactivity at different within one molecule. However, such "dual" has rarely been observed in the condensed phase. Herein we report isolation of crystalline 1λ2,3λ2-1-phosphonia-3-phosphinyl-cyclohex-4-enes 2a,b˙+, which can be considered delocalized DRCs were completely characterized by crystallographic, spectroscopic, computational methods. These contain a site seven six valence electrons, respectively, stabilized via conjugation, yet remain separated. They exhibit that differs from conventional (CRCs); specifically they sequential molecule solution.

Language: Английский

Citations

1
Electrochemical Decarboxylation Coupling Reactions DOI
Jiaxiu Liu, Haoran Li, Wei‐Si Guo

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(66)

Published: Oct. 16, 2024

Abstract Carboxylic acids are attractive synthetic feedstocks with stable, non‐toxic, and inexpensive properties that can be easily obtained from natural sources or through synthesis. have long been considered environmentally friendly coupling agents in various organic transformations. In recent years, electrochemically mediated decarboxylation reactions of decarboxylic their derivatives (NHPI) emerged as effective new methods for constructing carbon‐carbon carbon‐heterocarbon chemical bonds. Compared transition metal photochemistry‐mediated catalytic reactions, which do not require the addition oxidants strong bases, electrochemically‐mediated decarboxylative transformations a sustainable strategy. addition, functional groups tolerate electrochemical conversion strategy well. Here, we summarize to better elucidate advantages reactions.

Language: Английский

Citations

1
Predictive Models for Ligand Effects on a Reactive Al-Containing Radical Intermediate from Multivariate Linear Regression Analysis DOI
S. M. Supundrika Subasinghe, Maxim R. Radzhabov, Neal P. Mankad

et al.

Organometallics, Journal Year: 2024, Volume and Issue: 43(22), P. 2854 - 2861

Published: Nov. 11, 2024

Our lab has studied a complex with an Al–Fe bond capable of cooperative substrate activation processes. This reactivity was previously found to depend on homolytic dissociation followed by coordination the AlIII center resulting redox noninnocent radical intermediate. The current study investigates ligand influences free energy (BDFEAl–Fe) and Gibbs H2O at aluminum (ΔGOH2) for series variants systematic changes in their substitution patterns. DFT calculations combined multivariate linear regression analysis provided predictive models effects both BDFEAl–Fe ΔGAl–OH2 three synthetically tunable positions molecular architecture when using appropriate electronic (σpara, σmeta) steric (wSterimol, %Vbur) descriptors. Chemical interpretations were facilitated use these intuitive Linear scaling relationships relating ΔGOH2 further insight. We expect our findings inform designs future Al-containing heterobinuclear complexes small molecule processes cleavage reactions strong or inert bonds.

Language: Английский

Citations

1