Diverse Functionality of Molecular Germanium: Emerging Opportunities as Catalysts

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(35), P. 24209 - 24232

Published: Aug. 22, 2024

Fundamental research on germanium as the central element in compounds for bond activation chemistry and catalysis has achieved significant feats over last two decades. Designing strategies small molecule activations ultimate catalysts established capitalize orbital modalities of germanium, apparently imitating transition-metal frontier orbitals. There is a growing body examples contemporary implicating tunability orbitals through avant-garde approaches such geometric constrained empowered reactivity, bimetallic complementarity, cooperative etc. The goal this Perspective to provide readers with an overview emerging opportunities field germanium-based by perceiving underlying key principles. This will help convert discrete set findings into more systematic vision catalyst designs. Critical exposition germanium's participations evokes challenges involved innovative designs, wherein viewpoints are provided. We close addressing forward-looking directions catalytic manifold development. hope that be motivational applied constituent pragmatic catalysts.

Language: Английский

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Halonium and Chalconium Salt-Catalyzed Schiff Condensation: Kinetics and DFT Insights into Organocatalyst Activity Parameters

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Chalconium and halonium salts catalyze Schiff condensation. Kinetic data DFT calculations show that the catalytic activity correlates with maximum electrostatic potential on σ-holes, whereas other factors are less significant.

Language: Английский

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Porous Ceramic Nanofibrous Sponges for Fluoride Ion Removal from Contaminated Water

ACS Applied Nano Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

Language: Английский

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Hexaphenyl-1,2-Diphosphonium Dication [Ph₃P–PPh₃]²⁺: Superacid, Superoxidant, or Super Reagent?

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

Published: April 24, 2025

The oxidation of triphenylphosphine by perfluorinated phenaziniumF aluminate in difluorobenzene affords hexaaryl-1,2-diphosphonium dialuminate 1. Dication 12+ is valence isoelectronic with elusive hexaphenylethane, where instead the formation a mixture trityl radical and Gomberg's dimer favored. Quantum-chemical calculations combination Raman/IR spectroscopies rationalize stability P-P bonded suggest, akin to halogens, facile homolytic as well heterolytic scission. Thus, serves surrogate both triphenylphosphorandiylium dication (Ph3P2+) monocation (Ph3P·+). Treating 1 dimethylaminopyridine (DMAP) or tBu3P replaces under bond Qualifying superoxidant (E vs Fc/Fc+ = +1.44 V), oxidizes trimethylphosphine. Based on halide abstraction experiments (-BF4, -PF6, -SbCl6, -SbF6) deoxygenation triethylphosphine oxide, triflate anions toluic acid, also features Lewis superacidity. controlled hydrolysis Hendrickson's reagent, which itself finds broad use dehydration agent. Formally, scission occurs diphenyldisulfide (PhSSPh) triple bonds benzo- acetonitrile. irradiation light cleaves homolytically generates transient cations, engage H-atom CH phosphoranylation.

Language: Английский

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Halogen bonded associates of iodonium salts with 18-crown-6: does structural flexibility or structural rigidity of the σ-hole donor provide efficient substrate ligation?

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(29), P. 12929 - 12935

Published: Jan. 1, 2024

An acyclic diphenyliodonium cation forms stronger interactions with a bulky Lewis base than cyclic dibenziodolium cation.

Language: Английский

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Recent Trends in Triarylborane Chemistry: Diversification of Structures and Reactivity via meta-Substitution of the Aryl Groups

Synthesis, Journal Year: 2024, Volume and Issue: 56(22), P. 3421 - 3430

Published: Aug. 19, 2024

Abstract This Short Review summarizes the synthesis and applications of triarylboranes (BAr3), including both homoleptic heteroleptic species, with a focus on modification their electronic structural properties via introduction meta-substituents respect to B atoms Ar groups. approach constitutes complementary alternative conventional strategies for design BAr3, which are usually based ortho- and/or para-substituents. An initial analysis revealed that CH3 F most common in hitherto reported BAr3 (apart from H atom). Thus, an extensive exploration other substituents, e.g., heavier halogens, longer or functionalized alkyl groups, aryl will increase our knowledge structure reactivity eventually lead range new applications. 1 Introduction 2 Scope this 2.1 The Electronic Steric Influence meta-Substituents 2.2 Molecular Transformations Mediated by meta-Substituted Boranes 2.3 Other Examples meta-Functionalization 3 Conclusions Perspectives

Language: Английский

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1,4-Diphosphorinane Synthesis at a Cationic Aluminum(III) Center

Organometallics, Journal Year: 2024, Volume and Issue: 44(1), P. 148 - 157

Published: Dec. 18, 2024

Lewis acidic group 13 cations are useful mediators of small-molecule and catalytic reactivity alike. Previous work has elaborated on the use bulky β-diketiminate Al(III) for cycloaddition intermolecular coupling alkene substrates, giving new [Al]–C bonds. Motivated by a desire to prepare aluminum/phosphorus-containing ambiphilic ligands, here we probe intramolecular mono- diphosphines bearing pendent group. Despite drive Al–P bond formation (as shown control experiments), reaction specialized allyl-appended diphosphine results in rapid cyclization, producing an aluminum-bound 1,4-diphosphorinane (six-membered ring). Together, this contribution offers complementary route toward class molecule emphasizes importance substrate design characteristics such as phosphorus/alkene(β-carbon) linker length accessing productive cyclization. The subsequent heterocycle, including coordination chemistry with gold(I), additionally shared.

Language: Английский

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Low coordinate Zn(II) organocations bearing extremely bulky NHC ligands: structural features, air and water tolerance and use in hydrosilylation and hydrogenation catalysis.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(38), P. 15849 - 15858

Published: Jan. 1, 2024

Super bulky [(ITr)Zn(C 6 F 5 )] + cation is stable towards hydrolysis and reversibly coordinates water at room temperature. Despite its steric bulk, it an effective imine hydrogenation CO 2 hydrosilylation catalyst.

Language: Английский

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Amplifying Lewis Acidity by Oxidation: Leveraging the Redox-Activity of Bis(3,6-di-tert-butyl-catecholato)silane

Dalton Transactions, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 29, 2024

Oxidation boosts the potential of bis(catecholato)silanes, transforming them into Lewis superacidic radical cations with remarkable catalytic activity in dimerization, hydrodeoxygenation, and carbonyl-olefin metathesis.

Language: Английский

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The Ether‐Adduct of a Lewis Superacidic, Dicoordinate Aluminum Hydride Cation and the Ion Affinities of Solvent‐Adducts

Zeitschrift für anorganische und allgemeine Chemie, Journal Year: 2024, Volume and Issue: 650(21)

Published: June 18, 2024

Abstract Aluminum reagents are widely used as strong Lewis acids for organic transformations and catalysis. In recent years, a variety of Al‐Lewis superacids could be accessed by preparation aluminum cations paired with weakly‐coordinating anions or use perfluorinated substituents at the metal. While majority these is composed tricoordinate Al‐metal atom, examples dicoordinate Al species very scarce. this study, we report [(Mes*)Al(H)(OEt 2 )] + [Al(OR F ) 4 ] − (Mes*=2,4,6‐ t Bu 3 ‐C 6 H , R =C(CF reaction protonated ether [H(OEt [Mes*AlH . Structural analysis supported computed frontier orbitals atomic charges reveals that cation best described diethylether adduct [(Mes*)Al(H)] acts synthon to low‐coordinate cation. To incorporate masking coordination site ether, enthalpy dissociation included in fluoride‐ hydride ion affinities (XIA) entropic effects treated defining “free affinity” (fXIA), basing on Gibbs energy change. Hereby, acidity free well their solvent adducts can estimated.

Language: Английский

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