Inhibition of Alkali Metal Reduction of 1‐Adamantanol by London Dispersion Effects

Mears, Kristian L.; Stennett, Cary R.; Fettinger, James C.; Vasko, Petra; Power, Philip P.

doi:10.1002/anie.202201318

Cited by 9 publications

(10 citation statements)

References 40 publications

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“…Lately, these non‐covalent interactions have been found to be a factor towards the stabilization of theoretically calculated intermediates for bimetallic potassium‐aluminyl compounds, [29a,b] exhibiting interesting alkali‐metal‐mediated reactivity [30a,b] . A recent study by Power and co‐workers demonstrated the significance of LDF in the incomplete reduction of 1‐adamantol with alkali metals (Li, Na, and K) [31] . Having a series of group one aluminate structures at our disposal, we sought to quantify the interactions in the unsolvated complexes 1 , 2 , 3 , and 4 into electrostatic and dispersive components.…”

Section: Resultsmentioning

confidence: 99%

“…[ 30a , 30b ] A recent study by Power and co‐workers demonstrated the significance of LDF in the incomplete reduction of 1‐adamantol with alkali metals (Li, Na, and K). [31] Having a series of group one aluminate structures at our disposal, we sought to quantify the interactions in the unsolvated complexes 1 , 2 , 3 , and 4 into electrostatic and dispersive components. Attractive dispersion interactions are an important intermediate range class of stabilizing interactions in organometallic complexes.…”

Section: Resultsmentioning

confidence: 99%

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Hydrocarbon Soluble Alkali‐Metal‐Aluminium Hydride Surrog[ATES]

Banerjee

Macdonald

Orr

et al. 2022

Chemistry A European J

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A series of group 1 hydrocarbon-soluble donor free aluminates [AM( t BuDHP)(TMP)Al( i Bu) 2 ] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2-t BuC 5 H 5 N)AM)] containing a surrogate hydride (sp 3 CÀ H) with [( i Bu) 2 Al(TMP)]. These aluminates have been characterised by X-ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier alkali metal aluminates exist as polymeric chains propagated by non-covalent interactions between the alkali metal cations and the alkyldihydropyridyl units. Solvates [(THF)Li-( t BuDHP)(TMP)Al( i Bu) 2 ] and [(TMEDA)Na( t BuDHP)(TMP)Al( i Bu) 2 ] have also been crystallographically characterised. Theoretical calculations show how the dispersion forces tend to increase on moving from Li to Rb, as opposed to the electrostatic forces of stabilization, which are orders of magnitude more significant. Having unique structural features, these bimetallic compounds can be considered as starting points for exploring unique reactivity trends as alkali-metal-aluminium hydride surrog [ATES].

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Hydrocarbon Soluble Alkali‐Metal‐Aluminium Hydride Surrog[ATES]

Banerjee

Macdonald

Orr

et al. 2022

Chemistry A European J

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“…Interestingly, our synthetic routes to the anticipated monosubstituted alkali metal 1-adamantoxide (MOAd 1 , M = Li, Na, and K) afforded the three-coordinate species [M(OAd 1 )(HOAd 1 ) 2 ] (Figure ). The significance of this result illustrates the first example of LD interactions limiting the reduction potential of alkali metals, despite excess metal being employed. Energy decomposition analysis of this complex showed that the Ad 1 fragments afford significant dispersion stabilization (and are therefore good DED ligands): approximately one-third of the calculated total bonding energies could be assigned to dispersion effects within this molecule.…”

Section: Designing Enhanced Ld Effects In Hydrocarbon Ligandsmentioning

confidence: 99%

“…Interligand LD interactions from close contacts (orange lines) within the first alkali metal reduction-limited complex [Na(OAd 1 )(HOAd 1 ) 2 ]. Adapted with permission from ref . Copyright 2022 Wiley-VCH GmbH.…”

Section: Designing Enhanced Ld Effects In Hydrocarbon Ligandsmentioning

confidence: 99%

Beyond Steric Crowding: Dispersion Energy Donor Effects in Large Hydrocarbon Ligands

Mears

Power

2022

Acc. Chem. Res.

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Conspectus Interactions between sterically crowded hydrocarbon-substituted ligands are widely considered to be repulsive because of the intrusion of the electron clouds of the ligand atoms into each other’s space, which results in Pauli repulsion. Nonetheless, there is another interaction between the ligands which is less widely publicized but is always present. This is the London dispersion (LD) interaction which can occur between atoms or molecules in which dipoles can be induced instantaneously, for example, between the H atoms from the ligand C–H groups. These LD interactions are always attractive, but their effects are not as widely recognized as those of the Pauli repulsion despite their central role in the formation of condensed matter. Their relatively poor recognition is probably due to the relative weakness (ca. 1 kcal mol–1) of individual H···H interactions owing to their especially strong distance dependence. In contrast, where there are numerous H···H interactions, a collective LD energy equaling several tens of kcal mol–1 may ensue. As a result, in some molecules the latent importance of the LD attraction energies emerges and assumes a prominence that can overshadow the Pauli effects (e.g., in the stabilization of high-oxidation-state transition-metal alkyls, inducing disproportionation reactions, or in the stabilization of otherwise unstable bonds). Despite being known for over a century, the accurate quantification of individual H···H LD effects in molecular species is a relatively recent phenomenon and at present is based mainly on modified DFT calculations. A few leading reviews summarized these earlier studies of the C–H···H–C LD interactions in organic molecules, and their effects on the structures and stabilities were described. LD effects in sterically crowded inorganic and organometallic molecules have been recognized. The author’s interest in these LD effects arose fortuitously over a decade ago during research on sterically crowded heavier main-group element carbene analogues and two-coordinate, open-shell (d1–d9) transition-metal complexes where counterintuitive steric effects were observed. More detailed explanations of these effects were provided by dispersion-corrected DFT calculations in collaboration with the groups of Tuononen and Nagase (see below). This Account describes our development of these initial results for other inorganic molecular classes. More recently, the work has led us to move to the planned inclusion of dispersion effects in ligands to stabilize new molecular types with theoretical input from the groups of Vasko and Grimme (see below). Our approach sought to use what Grimme has described as dispersion effect donor (DED) groups (i.e., spatially close-lying, densely packed substituents either as ligands (e.g., −C6H2-2,4,6-Cy3, Cy = cyclohexyl) or as parts of ligands (e.g., a Cy substituent) that produce relatively large dispersion energies to stabilize these new compounds. We predict that the future design of sterically crowding hydrocarbon ligands will include the ...

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“…Theoretical studies further suggested that terpenes acting as DED ligands would provide valuable insight into LD effects in molecular complexes, and how structural conformations affect subsequent reactivity. The introduction of DED ligands has allowed the characterization of otherwise non-isolable species, [16][17][18][19][20][21] and DED ligands have also been shown to be important for understanding previously established reactivities, for example in the formation of alkoxides 22 or enzyme-relevant thiourea catalysts. 23 While larger ligands provide kinetic stabilization, many studies have demonstrated the importance of the underpinning LD interactions within these ligand frameworks which also give rise to stabilizing effects.…”

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confidence: 99%