Low oxidation state aluminum-containing cluster anions: Cp∗AlnH−, n = 1–3

Zhang, Xinxing; Ganteför, Gerd; Eichhorn, Bryan W.; Mayo, Dennis H.; Sawyer, William H.; Gill, Ann F.; Kandalam, Anil K.; Schnöckel, Hansgeorg; Bowen, Kit H.

doi:10.1063/1.4959847

Cited by 6 publications

(1 citation statement)

References 51 publications

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“…Because of this large gap between the 3s 2 and 3p 1 shells, it may be possible that in small clusters the valence of Al may be +1, leading to electronically stable clusters with unexpected stoichiometries. Al(I) compounds such as Al-cyclopentadiene and Al-halides have been used to form metalloid clusters, demonstrating that aluminum in the +1 oxidation state may be stabilized. − However, the question remains whether it is possible to obtain other stable Al n O m compositions that are electronically and energetically stable.…”

Section: Introductionmentioning

confidence: 99%

Multiple-Valence Aluminum and the Electronic and Geometric Structure of Al_nO_m Clusters

Armstrong

Reber

2019

J. Phys. Chem. A

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Electronic stability in aluminum clusters is typically associated with either closed electronic shells of delocalized electrons or a +3 oxidation state of aluminum. To investigate whether there are alternative routes toward electronic stability in aluminum oxide clusters, we used theoretical methods to examine the geometric and electronic structure of Al n O m (2 ≤ n ≤ 7; 1 ≤ m ≤ 10) clusters. Electronically stable clusters with large HOMO–LUMO (highest occupied molecular orbital and lowest unoccupied molecular orbital) gaps were identified and could be grouped into two categories. (1) Al2n O3n clusters with a +3 oxidation state on the aluminum and (2) planar clusters including Al4O4, Al5O3, Al6O5, and Al6O6. The structures of the planar clusters have external Al atoms bound to a single O atom. Their electronic stability is explained by the multiple-valence Al sites, with the internal Al atoms having an oxidation state of +3, whereas the external Al atoms have an oxidation state of +1.

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Section: Introductionmentioning

confidence: 99%

Multiple-Valence Aluminum and the Electronic and Geometric Structure of Al_nO_m Clusters

Armstrong

Reber

2019

J. Phys. Chem. A

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Improved barrier parameters and working stability of Au/p-GO/n-lnP/Au–Ge Schottky barrier diode with GO interlayer showing resistive switching effect

Baltakesmez

2019

Vacuum

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The Role of Ligand Steric Bulk in New Monovalent Aluminum Compounds

et al. 2017

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The tetrameric Al(I) cyclopentadienyl compound AlCp* (Cp* = CMe) is a prototypical low-valence Al compound, with delocalized bonding between four Al(I) atoms and η ligands bound to the cluster exterior. The synthesis of new [AlR] (R = CMePr, CMeiPr) tetramers is presented. Though these systems failed to crystallize, comparison of variable-temperature Al NMR data with density functional theory (DFT) calculations indicate that these are AlR tetramers analogous to AlCp* but with increased ligand steric bulk. NMR, DFT, and Atoms in Molecules analyses show that these clusters are enthalpically more stable as tetramers than the Cp* variant, due in part to noncovalent interactions across the bulkier ligand groups. Thermochemistry calculations for the low-valence metal interactions were found to be extremely sensitive to the DFT methodology used; the M06-2X functional with a cc-pVTZ basis set is shown to provide very accurate values for the enthalpy of tetramerization and Al NMR shifts. This computational method is then used to predict geometrical structures, noncovalent ligand interactions, and monomer/tetramer equilibrium in solution for a series of Al(I) cyclopentadienyl compounds of varying steric bulk.

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Low oxidation state aluminum-containing cluster anions: Cp∗AlnH−, n = 1–3

Cited by 6 publications

References 51 publications

Multiple-Valence Aluminum and the Electronic and Geometric Structure of Al_nO_m Clusters

Multiple-Valence Aluminum and the Electronic and Geometric Structure of Al_nO_m Clusters

Improved barrier parameters and working stability of Au/p-GO/n-lnP/Au–Ge Schottky barrier diode with GO interlayer showing resistive switching effect

The Role of Ligand Steric Bulk in New Monovalent Aluminum Compounds

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Low oxidation state aluminum-containing cluster anions: Cp∗AlnH−, n = 1–3

Cited by 6 publications

References 51 publications

Multiple-Valence Aluminum and the Electronic and Geometric Structure of AlnOm Clusters

Multiple-Valence Aluminum and the Electronic and Geometric Structure of AlnOm Clusters

Improved barrier parameters and working stability of Au/p-GO/n-lnP/Au–Ge Schottky barrier diode with GO interlayer showing resistive switching effect

The Role of Ligand Steric Bulk in New Monovalent Aluminum Compounds

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Product

Resources

About

Multiple-Valence Aluminum and the Electronic and Geometric Structure of Al_nO_m Clusters

Multiple-Valence Aluminum and the Electronic and Geometric Structure of Al_nO_m Clusters