Trapping an Unusual Pentacoordinate Carbon Atom in a Neutral Trialuminum Complex

Villegas‐Escobar, Nery; Martı́nez, Javier; Matute, Ricardo A.; Saltarini, Sebastian; daniluc, constantin G.; Gade, Lutz H.; Rojas, René S.

doi:10.26434/chemrxiv.14552553.v2

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References 19 publications

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“…Gibbs free energy differences (Δ G ) were reported as where Δ E is the difference in electronic energies, and Δ G RRHO T collects the zero-point vibrational energy (ZPVE) and RRHO Gibbs free energy corrections. Gibbs free energy and ZPVE corrections were computed using a Python script developed by one of the authors . Unfortunately, it was not possible to include solvent effects in the calculations due to the lack of an exact dielectric constant for this nonconventional solvent ( 4a ).…”

Section: Methodsmentioning

confidence: 99%

Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO₂ Fixation into Cyclic Carbonates

et al. 2020

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A new iodide aluminum complex ({AlI(κ4-naphbam)}, 3) supported by a tetradentate amidinate ligand derived from a naphthalene-1,8-bisamidine precursor (naphbamH, 1) was obtained in quantitative yield via reaction of the corresponding methyl aluminum complex ({AlMe(κ4-naphbam)}, 2) with 1 equiv of I2 in CH2Cl2 at room temperature. Complexes 2 and 3 were tested and found to be active as catalysts for the cyclic carbonate formation from epoxides at 80 °C and 1 bar of CO2 pressure. A first series of experiments were carried out with 1.5 mol % of the alkyl complex 2 and 1.5 mol % of tetrabutylammonium iodide (TBAI) as a cocatalyst; subsequently, the reactions were carried out with 1.5 mol % of iodide complex 3 as a single-component catalyst. Compound 3 is one of the first examples of a nonzwitterionic halide single-component aluminum catalyst producing cyclic carbonates. The full catalytic cycle with characterization of all minima and transition states was characterized by quantum chemistry calculations (QCCs) using density functional theory. QCCs on the reaction mechanism support a reaction pathway based on the exchange of the iodine contained in the catalyst by 1 equiv of epoxide, with subsequent attack of I– to the epoxide moiety producing the ring opening of the epoxide. QCCs triggered new insights for the design of more active halide catalysts in future explorations of the field.

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Section: Methodsmentioning

confidence: 99%

Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO₂ Fixation into Cyclic Carbonates

et al. 2020

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Trapping an Unusual Pentacoordinate Carbon Atom in a Neutral Trialuminum Complex

Cited by 1 publication

References 19 publications

Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO₂ Fixation into Cyclic Carbonates

Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO₂ Fixation into Cyclic Carbonates

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Trapping an Unusual Pentacoordinate Carbon Atom in a Neutral Trialuminum Complex

Cited by 1 publication

References 19 publications

Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO2 Fixation into Cyclic Carbonates

Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO2 Fixation into Cyclic Carbonates

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Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO₂ Fixation into Cyclic Carbonates

Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO₂ Fixation into Cyclic Carbonates