Recent Developments in the Syntheses of Aluminum Complexes Based on Redox-Active Ligands

Gahlaut, Puneet Singh; Yadav, K. S.; Gautam, Deepak; Jana, Barun

doi:10.1016/j.jorganchem.2022.122298

Cited by 8 publications

(9 citation statements)

References 86 publications

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“…This breadth of success is in contrast to the element-ligand cooperative (ELC) chemistry of the main-group elements, which has been much less developed . We have been investigating the coordination chemistry of aluminum and other group 13 metal complexes supporting redox-active and/or noninnocent ligand frameworks, , and specifically, have an interest in understanding the role that the complexes play in ELC chemistry.…”

Section: Introductionmentioning

confidence: 99%

Reversible O–H Bond Activation by Tripodal tris(Nitroxide) Aluminum and Gallium Complexes

Scott,

Maenaga,

Woodside

et al. 2024

Inorg. Chem.

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Herein, we report the preparation and characterization of the Group 13 metal complexes of a tripodal tris(nitroxide)-based ligand, designated (TriNOx 3− )M (M = Al (1), Ga (2), In (3)). Complexes 1 and 2 both activate the O−H bond of a range of alcohols spanning a ∼10 pK a unit range via an element-ligand cooperative pathway to afford the zwitterionic complexes (HTriNOx 2− )M−OR. Structures of these alcohol adduct products are discussed. We demonstrate that the thermodynamic and kinetic aspects of the reactions are both influenced by the identity of the metal, with 1 having higher reaction equilibrium constants and proceeding at a faster rate relative to 2 for any given alcohol. These parameters are also influenced by the pK a of the alcohol, with more acidic alcohols reacting both to more completion and faster than their less acidic counterparts. Possible mechanistic pathways for the O−H activation are discussed.

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Section: Introductionmentioning

confidence: 99%

Reversible O–H Bond Activation by Tripodal tris(Nitroxide) Aluminum and Gallium Complexes

Scott,

Maenaga,

Woodside

et al. 2024

Inorg. Chem.

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“…have a great potential for stabilization of molecular alumoxanes. 8 Further, the use of bulky N,N-chelating ligands in the chemistry of non-transition metals made it poss-ible to obtain very interesting data on their reactivity [9][10][11][12][13] and catalytic activity. [14][15][16][17] Most of the alumoxanes stabilized by bulky ligands are dimeric molecules with one or two oxobridges.…”

Section: Introductionmentioning

confidence: 99%

Diversity of transformation of heteroallenes on acenaphthene-1,2-diimine aluminum oxide

Koptseva,

Skatova,

Moskalev

et al. 2024

Dalton Trans.

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“…Consequently, a recent goal of synthetic chemists is to mimic transition metal-like reactivity with aluminum, taking a glance at future applications in catalysis. [4,5] While Lewis acid catalysis with aluminum is a historical field of chemistry, [6] redox-mediated catalyses are scarce due to the energetic gradient between sub-and high-valent oxidation states. [7] The vivid field of Main Group redox chemistry in general, [7,8] and subvalent aluminum chemistry in particular, clearly reflects the interest in approaching aluminum redox cycles in the future.…”

Section: Introductionmentioning

confidence: 99%

Visible‐Light Activation of Diorganyl Bis(pyridylimino) Isoindolide Aluminum(III) Complexes and Their Organometallic Radical Reactivity

Wenzel,

Werner,

Allgaier

et al. 2024

Angew Chem Int Ed

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We report on the synthesis and characterization of a series of (mostly) air‐stable diorganyl bis(pyridylimino) isoindolide (BPI) aluminum complexes and their chemistry upon visible‐light excitation. The redox non‐innocent BPI pincer ligand allows for efficient charge transfer homolytic processes of the title compounds. This makes them a universal platform for the generation of carbon‐centered radicals. The photo‐induced homolytic cleavage of the Al–C bonds was investigated by means of stationary and transient UV/Vis spectroscopy, spin trapping experiments, as well as EPR and NMR spectroscopy. The experimental findings were supported by quantum chemical calculations. Reactivity studies enabled the utilization of the aluminum complexes as reactants in tin‐free Giese‐type reactions and carbonyl alkylations under ambient conditions, which both indicated radical‐polar crossover behavior. A deeper understanding of the physical fundamentals and photochemical process was provided, furnishing in turn a new strategy to control the reactivity of bench‐stable aluminum organometallics.

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Recent Developments in the Syntheses of Aluminum Complexes Based on Redox-Active Ligands

Cited by 8 publications

References 86 publications

Reversible O–H Bond Activation by Tripodal tris(Nitroxide) Aluminum and Gallium Complexes

Reversible O–H Bond Activation by Tripodal tris(Nitroxide) Aluminum and Gallium Complexes

Diversity of transformation of heteroallenes on acenaphthene-1,2-diimine aluminum oxide

Visible‐Light Activation of Diorganyl Bis(pyridylimino) Isoindolide Aluminum(III) Complexes and Their Organometallic Radical Reactivity

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