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Coupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether‐Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure–Reactivity Relationship and Mechanistic DFT Study
Author(s) -
Della Monica Francesco,
Vummaleti Sai V. C.,
Buonerba Antonio,
Nisi Assunta De,
Monari Magda,
Milione Stefano,
Grassi Alfonso,
Cavallo Luigi,
Capacchione Carmine
Publication year - 2016
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201600621
Subject(s) - chemistry , catalysis , thioether , reactivity (psychology) , propylene oxide , ligand (biochemistry) , bimetallic strip , catalytic cycle , propylene carbonate , synergistic catalysis , epoxide , coupling reaction , carbon dioxide , photochemistry , inorganic chemistry , organic chemistry , ethylene oxide , medicine , biochemistry , alternative medicine , receptor , electrode , pathology , electrochemistry , copolymer , polymer
A series of dinuclear iron(III) I complexes supported by thioether‐triphenolate ligands have been prepared to attain highly Lewis acidic catalysts. In combination with tetrabutylammonium bromide (TBAB) they are highly active catalysts in the synthesis of cyclic organic carbonates through the coupling of carbon dioxide to epoxides with the highest initial turnover frequencies reported to date for the conversion of propylene oxide to propylene carbonate for iron‐based catalysts (5200 h −1 ; 120 °C, 2 MPa, 1 h). In particular, these complexes are shown to be highly selective catalysts for the coupling of carbon dioxide to internal oxiranes affording the corresponding cyclic carbonates in good yield and with retention of the initial stereochemical configuration. A density functional theory (DFT) investigation provides a rational for the relative high activity found for these Fe(III) complexes, showing the fundamental role of the hemilabile sulfur atom in the ligand skeleton to promote reactivity. Notably, in spite of the dinuclear nature of the catalyst precursor only one metal center is involved in the catalytic cycle.