NHC Aluminum Chemistry on the Rise

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(40), P. 16436 - 16454

Published: Jan. 1, 2024

This review highlights recent developments of the use N -heterocyclic carbenes (NHCs) in alane and aluminum organyl chemistry.

Language: Английский

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Redox Non-Innocent Bis-Silylene Aluminium Complexes with a Carborane Backbone

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

[AlI 2 + ] complexes of a bis-silylenyl carborane have been synthesised with three interconvertible ligand oxidation states. Further reduction using K(C 10 H 8 ) furnishes 1,4-naphthalene derivatives, indicative low state Al intermediates.

Language: Английский

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Dicationic Boron Derivatives of Schlenk’s and Thiele’s Hydrocarbon

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

Published: March 19, 2025

In recent years, neutral NHC-stabilized boryl radicals have been investigated as reactive species in various organic transformations. However, cationic boron significantly less explored. addition, boron-centered open-shell with S > 1/2 emerged attractive synthetic targets. this study, we provide a route to an radical cation salt of the weakly coordinating [Al(ORF)4]- (RF = C(CF3)3) anion. The procedure was extended dicationic diboron derivatives Schlenk's and Thiele's hydrocarbons meta- para-phenylene coupling units between spin centers. While most known isolable biradicals singlet ground-state thermally accessible triplet state, version hydrocarbon occupies spin-state, shown by combined electron paramagnetic resonance spectroscopy density functional theory studies. Furthermore, initial reactivity studies dications elemental sulfur diphenyldiselenide are presented.

Language: Английский

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Molecular Design of Al(II) Intermediates for Small Molecule Activation

JACS Au, Journal Year: 2025, Volume and Issue: 5(5), P. 2076 - 2088

Published: May 8, 2025

Promoting societally important small molecule activation processes with earth-abundant metals is foundational for a sustainable chemistry future. In this context, mapping new reaction pathways that would enable abundant main-group elements to mimic the behaviors of d- and f-block facilitated by exploring unusual oxidation states. The most metal on earth, aluminum, has been well studied in Lewis acidic +III basic +I states but rarely potentially biphilic +II state until recently, when renaissance Al-(II) emerged from range research groups. Perspective, we review mononuclear Al radicals, including both Al-centered radicals (i.e., compounds) redox non-innocent systems formally species are physically Al-(III) ligand-centered radicals), an emphasis reactivity. We also provide meta-analysis literature summarize how different design strategies (e.g., non-innocence, strained coordination geometries) have shown impart character tune their behavior, thus allowing certain ions such as Ti-(III) Sm-(II). expect these molecular concepts inform future studies continues grow.

Language: Английский

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Synthesis and Reactivity of an Alumanyl–Tin Species to Form an Al,N-Heteroallene Derivative

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(42), P. 28653 - 28657

Published: Oct. 8, 2024

The molecular chemistry of metal–metal bonds is crucial for understanding the bonding and reactivity metal-containing molecules as well solid metals their alloys, especially with respect to application catalysts organic transformations industrial processes. Despite high efficiency recently developed nucleophilic alumanyl anions in synthesis diverse Al–metal bonds, between main group a low oxidation state Al atom remains largely unexplored. This paper describes reaction an anion chlorostannylene precursor afford compound unprecedented covalent Al–Sn bond. lability bond renders it reactive toward insertion carbodiimide, N2O, phenylacetylene. Remarkably, benzonitrile furnished Al,N-heteroallene species that contains linear Al═N═C linkage.

Language: Английский

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A Discrete Trialane with a Near-Linear Al₃ Axis

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

Published: Nov. 26, 2024

The presence of inherent electronic unsaturation in aluminum predominantly results the formation clusters, with very few examples compounds containing discrete chains atoms existence. In this work, we present successful synthesis and structural authentication a highly unusual trialane species near-linear chain three Al atoms, alongside carbene-stabilized aluminyl anion ([LAlR2]−), an alternative product produced by varying reaction conditions. Quantum-chemical calculations have been applied to elucidate structure bonding these novel compounds. Additionally, successfully trapped intermediate using alkyne, suggesting intermediacy base-stabilized monomeric alumylene (LRAl:), which is also investigated through computational methods.

Language: Английский

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An Open-Shell Functionalization of Inorganic Benzene

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(48), P. 32906 - 32911

Published: Nov. 20, 2024

A borazine derivative functionalized by nitroxide free radicals,

Language: Английский

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Synthesis of An Unsymmetrical Dialumane and Kinetic Analysis of Its Alkene Insertion

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 5, 2024

An unsymmetrical dialumane was synthesized by the reaction of a nucleophilic alumanyl anion with bromoalumane and it structurally characterized to show existence Et

Language: Английский

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