Synthesis, Structure, and Properties of Al(Rbpy)3 Complexes (R = t-Bu, Me): Homoleptic Main-Group Tris-bipyridyl Compounds

DeCarlo, Samantha; Mayo, Dennis H.; Tomlinson, Warren; Hu, Jiangsheng; Hooper, Joseph P.; Zavalij, Peter; Bowen, Kit H.; Schnöckel, Hansgeorg; Eichhorn, Bryan W.

doi:10.1021/acs.inorgchem.6b00034

Cited by 16 publications

(10 citation statements)

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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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“…As a result, C 60 has eight accessible oxidation states that can be generated in solution. While multi-oxidation-state coordination complexes are known, such as the M(bipyridine) 3 complexes, , the redox activity is primarily ligand based, and electron correlation is limited. The redox behavior of C 60 and its fullerene relatives is unique and tied to the orbital degeneracies associated with their high-symmetry structures.…”

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confidence: 99%

Sb@Ni₁₂@Sb₂₀^–/+ and Sb@Pd₁₂@Sb₂₀ⁿ Cluster Anions, Where n = +1, −1, −3, −4: Multi-Oxidation-State Clusters of Interpenetrating Platonic Solids

et al. 2017

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KSb and KSb Zintl ion precursors react with Pd(PPh) in ethylenediamine/toluene/PBu solutions to give crystals of Sb@Pd@Sb/PBu salts, where n = 3, 4. The clusters are structurally identical in the two charge states, with nearly perfect I point symmetry, and can be viewed as an Sb@Pd icosahedron centered inside of an Sb dodecahedron. The metric parameters suggest very weak Sb-Sb and Pd-Pd interactions with strong radial Sb-Pd bonds between the Sb and Pd shells. All-electron DFT analysis shows the 3- ion to be diamagnetic with I symmetry and a 1.33 eV HOMO-LUMO gap, whereas the 4- ion undergoes a Jahn-Teller distortion to an S = 1/2 D structure with a small 0.1 eV gap. The distortion is predicted to be small and is not discernible by crystallography. Laser desorption-ionization time-of-flight mass spectrometry (LDI-TOF MS) studies of the crystalline samples show intense parent Sb@Pd@Sb ions (negative ion mode) and Sb@Pd@Sb (positive ion mode) along with series of Sb@Pd@Sb ions. Ni(cyclooctadiene) reacts with KSb in en/tol/BuPBr solvent mixtures to give black precipitates of Sb@Ni@Sb salts that give similar Sb@Ni@Sb parent ions and Sb@Ni@Sb degradation series in the respective LDI-TOF MS studies. The solid-state and gas-phase studies of the icosahedral Sb@M@Sb ions show that the clusters can exist in the -4, -3, -1, +1 (M = Pd) and +1, -1 (M = Ni) oxidation states. These multiple-charge-state clusters are reminiscent of redox-active fullerenes (e.g., C, where n = +1, 0, -1, -2, -3, -4, -5, -6).

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“…Several classes of aluminum complexes supporting redox-active ligands have been prepared. The majority of these systems have involved ligands incorporating nitrogen heteroatoms (Figure ) that have included complexes of 2,2′-bipyridine, , iminopyridine, − and bis(imino)pyridine ligands. − Our work in this field has focused on investigating the coordination chemistry of N -aryl-substituted α-diimine ligands [ArNC(CH 3 )C(CH 3 )NAr] to aluminum. Our interest in this class of ligands is 2-fold.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Neutral Ligand α-Diimine Complexes of Aluminum with Tunable Redox Energetics

et al. 2018

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The synthesis and full characterization of a series of neutral ligand α-diimine complexes of aluminum are reported. The compounds [Al(L)Cl)][AlCl] [L = N, N'-bis(4-R-CH)-2,3-dimethyl-1,4-diazabutadiene] are structurally analogous, as determined by multinuclear NMR spectroscopy and solid-state X-ray diffraction, across a range of electron-donating [R = Me (2), Bu (3), OMe (4), and NMe (5)] and electron-withdrawing [R = Cl (6), CF (7), and NO (8)] substituents in the aryl side arm of the ligand. UV-vis absorption spectroscopy and electrochemistry were used to access the optical and electrochemical properties, respectively, of the complexes. Both sets of properties are shown to be dependent on the R substituent. Density functional theory calculations performed on the [Al(L)Cl)][AlCl] complex (1) indicate primarily ligand-based frontier orbitals and were used to help support our discussion of both the spectral and electrochemical data. We also report the reaction of the L ligand with both AlBr and AlI and demonstrate a different reactivity profile for the heavier halide relative to the lighter members of the group.

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Synthesis, Structure, and Properties of Al(^Rbpy)₃ Complexes (R = t-Bu, Me): Homoleptic Main-Group Tris-bipyridyl Compounds

Cited by 16 publications

References 59 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

Sb@Ni₁₂@Sb₂₀^–/+ and Sb@Pd₁₂@Sb₂₀ⁿ Cluster Anions, Where n = +1, −1, −3, −4: Multi-Oxidation-State Clusters of Interpenetrating Platonic Solids

Synthesis and Characterization of Neutral Ligand α-Diimine Complexes of Aluminum with Tunable Redox Energetics

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Synthesis, Structure, and Properties of Al(Rbpy)3 Complexes (R = t-Bu, Me): Homoleptic Main-Group Tris-bipyridyl Compounds

Cited by 16 publications

References 59 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

Sb@Ni12@Sb20–/+ and Sb@Pd12@Sb20n Cluster Anions, Where n = +1, −1, −3, −4: Multi-Oxidation-State Clusters of Interpenetrating Platonic Solids

Synthesis and Characterization of Neutral Ligand α-Diimine Complexes of Aluminum with Tunable Redox Energetics

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Synthesis, Structure, and Properties of Al(^Rbpy)₃ Complexes (R = t-Bu, Me): Homoleptic Main-Group Tris-bipyridyl Compounds

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

Sb@Ni₁₂@Sb₂₀^–/+ and Sb@Pd₁₂@Sb₂₀ⁿ Cluster Anions, Where n = +1, −1, −3, −4: Multi-Oxidation-State Clusters of Interpenetrating Platonic Solids