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

Saltarini, Sebastián and Villegas-Escobar, Nery and Martínez, Javier and Daniliuc, Constantin G. and Matute, Ricardo A. and Gade, Lutz H. and Rojas, René S. (2021) Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO₂ Fixation into Cyclic Carbonates. Inorganic Chemistry, 60 (2). pp. 1172-1182. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20210104-164232160

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Abstract

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.inorgchem.0c03290DOIArticle
ORCID:
AuthorORCID
Villegas-Escobar, Nery0000-0002-6370-617X
Martínez, Javier0000-0002-1538-0689
Daniliuc, Constantin G.0000-0002-6709-3673
Matute, Ricardo A.0000-0002-0644-3799
Gade, Lutz H.0000-0002-7107-8169
Rojas, René S.0000-0002-5292-0816
Alternate Title:Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO2 Fixation into Cyclic Carbonates
Additional Information:© 2020 American Chemical Society. Received: November 5, 2020; Published: December 29, 2020. This work was supported by FONDECYT, Project Nos. 1161091 and 1200748. J.M. acknowledges funding from the CONICYT/FONDECYT Postdoctorate Project (No. 3180073). N.V-.E. and R.A.M. acknowledge financial support from FONDECYT grant 1181260. Powered@NLHPC: This research was partially supported by the supercomputing infrastructure of the NLHPC (ECM-02). R.S.R. thanks the Alexander von Humboldt Foundation for support through a reinvitation fellowship. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT)1161091
Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT)1200748
Comisión Nacional de Investigación Científica y Tecnológica (CONICYT)3180073
Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT)1181260
Alexander von Humboldt FoundationUNSPECIFIED
Issue or Number:2
Record Number:CaltechAUTHORS:20210104-164232160
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210104-164232160
Official Citation:Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO2 Fixation into Cyclic Carbonates. Sebastián Saltarini, Nery Villegas-Escobar, Javier Martínez, Constantin G. Daniliuc, Ricardo A. Matute, Lutz H. Gade, and René S. Rojas. Inorganic Chemistry 2021 60 (2), 1172-1182; DOI: 10.1021/acs.inorgchem.0c03290
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:107312
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:05 Jan 2021 15:33
Last Modified:19 Jan 2021 23:54

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