Mono-and Dinuclear Asymmetric Aluminum Guanidinates for the Catalytic CO2 Fixation into Cyclic Carbonates Rios Perez, Yersica Rodríguez Diéguez, Antonio This work was supported by FONDECYT, Project No. 1200748. Y.R.Y. acknowledges funding from Pontificia Universidad Catolica de Chile via a VRI 2015 -2017 fellowship and Ph.D. CONICYT 2018 fellowship No. 21182120. A.M.-S. acknowledges funding from Ph.D. CONICYT fellowship No. 51150322. The authors also gratefully acknowledge financial support from the Ministerio de Ciencia e Innovacion, Spain (grant numbers CTQ2016-77614-P and RED2018-102387-T) and "Plan Propio de I + D + i" of the Universidad Castilla-La Mancha (grant number 2020-GRIN29078). A set of trisubstituted guanidine ligands L1H2-L4H2 with general formula (PrHN)(2)CNR (R = Ph (L1H2), R = 2,4,6-Me3C6H2(L2H2), R = p-BrC6H4(L3H2), R = (C5H4)Fe(C5H5), Fc (L4H2)) was employed to synthesize a family of mono- and dinuclear asymmetric methyl aluminum guanidinato compounds ((L2H)AlMe2 (1), (L4H)AlMe2 (2), (L-1)Al2Me4 (3), (L-2)Al2Me4 (4), (L-3)Al2Me4 (5), (L-4)Al2Me4 (6), (L1H)(2)AlMe (7), (L2H)(2)AlMe (8), and (L4H)(2)AlMe (9)) that were characterized by NMR spectroscopy (1-9) and single-crystal X-ray diffraction (4 and 8). These compounds were tested as catalysts for the fixation of carbon dioxide with epoxides to give cyclic carbonates, using tetrabutylammonium iodide (TBAI) as cocatalyst. The reactions were performed under solvent-free conditions at 70 degrees C and 1 bar CO2 pressure. Complexes 1-9 were more active than their respective free guanidines under the same experimental conditions for the synthesis of styrene carbonate (11a). The dinuclear complex 6 was the most efficient and active catalyst for the synthesis of several monosubstituted carbonates (11a-1) with excellent conversions and selectivities. Furthermore, the formation of some disubstituted cyclic carbonates (13a-c) using this dinuclear aluminum catalyst was also studied. 2021-10-07T11:39:23Z 2021-10-07T11:39:23Z 2021-08-23 info:eu-repo/semantics/article Rios Perez, Y..[et al.]Mono-and Dinuclear Asymmetric Aluminum Guanidinates for the Catalytic CO2 Fixation into Cyclic Carbonates. Organometallics 2021, 40, 16, 2859–2869 Publication Date:August 5, 2021 [https://doi.org/10.1021/acs.organomet.1c00319] http://hdl.handle.net/10481/70722 10.1021/acs.organomet.1c00319 eng http://creativecommons.org/licenses/by/3.0/es/ info:eu-repo/semantics/openAccess Atribución 3.0 España ACS