Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO<sub>2</sub> Fixation into Cyclic Carbonates

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dc.contributor.authorSaltarini, Sebastian
dc.contributor.authorVillegas-Escobar, Nery
dc.contributor.authorMartinez, Javier
dc.contributor.authorDaniliuc, Constantin G.
dc.contributor.authorMatute, Ricardo A.
dc.contributor.authorGade, Lutz H.
dc.contributor.authorRojas, Rene S.
dc.date.accessioned2025-01-20T23:50:34Z
dc.date.available2025-01-20T23:50:34Z
dc.date.issued2021
dc.description.abstractA new iodide aluminum complex ({AlI(kappa(4)-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(kappa(4)-naphbam)}, 2) with 1 equiv of I-2 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 degrees 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.
dc.fuente.origenWOS
dc.identifier.doi10.1021/acs.inorgchem.0c03290
dc.identifier.eissn1520-510X
dc.identifier.issn0020-1669
dc.identifier.urihttps://doi.org/10.1021/acs.inorgchem.0c03290
dc.identifier.urihttps://repositorio.uc.cl/handle/11534/94728
dc.identifier.wosidWOS:000643574200070
dc.issue.numero2
dc.language.isoen
dc.pagina.final1182
dc.pagina.inicio1172
dc.revistaInorganic chemistry
dc.rightsacceso restringido
dc.titleToward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO<sub>2</sub> Fixation into Cyclic Carbonates
dc.typeartículo
dc.volumen60
sipa.indexWOS
sipa.trazabilidadWOS;2025-01-12
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