Browsing by Author "Maerten, Eddy"

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    New Aluminum Complexes with an Asymmetric Amidine–Imine Ligand: Synthesis, Characterization, and Application in Catalysis
    Gómez Zamorano, Fernando; Rojas Moraga, María José; Mallet-Ladeira, Sonia; Cabrera, Alan R.; Garo, Jordan; Sotiropoulos, Jean-Marc; Maerten, Eddy; Madec, David; Rojas, René S.
    In this work, a new asymmetric amidine–imine ligand, using 1,8-diaminonaphthalene as a rigid platform, was synthesized and characterized, and its ability to form complexes with aluminum(III) was investigated. Several aluminum complexes were synthesized and characterized in solution and in the solid state. The synthesis of a dihalogenated aluminum(III) complex (AlI2L) using a reducing agent revealed an atypical pathway, which was investigated using Density Functional Theory (DFT). The dimethylated aluminum complex AlMe2L and the dihalogenated aluminum complex AlI2L were evaluated as catalysts for the transformation of CO2 and epoxides into cyclic carbonates in the presence of Bu4NI as a co-catalyst or in a single-component system, respectively. AlMe2L/Bu4NI appeared to be the most efficient system under 1 bar of CO2 at 90 °C.
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    Synthesis and structures of homoleptic germylenes and stannylenes with sulfonimidamide ligands
    (2023) Lentz, Nicolas; Sodreau, Alexandre; Acuna, Alejandra; Mallet-Ladeira, Sonia; Maerten, Eddy; Sotiropoulos, Jean-Marc; Rojas Guerrero, Rene Segundo; Madec, David
    An unusual series of germylenes and stannylenes with homoleptic symmetric and unsymmetric N-substituted sulfonimidamide ligands PhSO(NiPr)(NHiPr) 1 and PhSO(NMes)(NHiPr) 2 have been prepared by protonolysis reaction of Lappert's metallylenes [M(HMDS)(2)] (M = Ge or Sn) with two equivalents of the appropriate sulfonimidamide. The homoleptic germylenes [PhSO(NiPr)(2)](2)Ge 3 and [PhSO(NMes)(NiPr)](2)Ge 4, and stannylenes [PhSO(NiPr)(2)](2)Sn 5 and [PhSO(NMes)(NiPr)](2)Sn 6 were fully characterized by NMR spectroscopy and by X-ray diffraction analysis. DFT calculations have been performed to understand the electronic properties brought by the sulfonimidamide ligand.
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    Tetra- and penta-coordinated aluminum complexes with bis-amidine ligands and their reactivity for efficient CO2 transformation to cyclic carbonates
    (Royal Society of Chemistry, 2025) Acuña, Alejandra; Villegas, Nery Andrés; Gómez Zamorano, Fernando Eduardo; Keim Gyllen, Nicole Catalina; Mallet-Ladeira, Sonia; Maerten, Eddy; Madec, David; Rojas Guerrero, René
    The development of efficient catalysts for CO2 transformation into value-added products is crucial for sustainable chemistry. In this work, we report the synthesis and characterization of a new series of tetra- and penta-coordinated aluminum complexes supported by bis-amidine ligands featuring a rigid naphthalene bridge and their application as catalysts in the reaction of carbon dioxide with epoxides to form cyclic carbonates. Interestingly, while tetra- and penta-coordinated aluminum complexes bearing methyl groups are efficient when used with TBAI as a co-catalyst, their iodo analogs proved to be inefficient in mono-component catalysis, requiring the use of additional TBAI. Computational results of the proposed systems reveal the necessity of achieving a delicate balance between the nucleophilic properties of iodide atoms and the steric configuration of the complexes. Experimental and computational studies offer valuable insights into the role of ligand structure in aluminum-based catalysts, highlighting the potential of main-group metals in CO2 fixation.