An Efficient and Versatile Lanthanum Heteroscorpionate Catalyst for Carbon Dioxide Fixation into Cyclic Carbonates

Abstract

A new lanthanum heteroscorpionate complex has shown exceptional catalytic activity for the synthesis of cyclic carbonates from epoxides and carbon dioxide. This catalyst system also promotes the reaction of bio-based epoxides to give an important class of bis(cyclic carbonates) that can be further used for the production of bio-derived non-isocyanate polyurethanes. The catalytic process requires low catalyst loading and mild reaction conditions for the synthesis of a wide range of cyclic carbonates.

Synthesis of Bio‐Based Cyclic Carbonates Using a Bio‐Based Hydrogen Bond Donor: Application of Ascorbic Acid to the Cycloaddition of CO2 to Oleochemicals

“…Use of CaI 2 /PPh 3 /dicyclohexyl‐functionalized 18‐crown‐6 ether (DCFCE) led to carbonation of EMO at low temperature (45 °C) under 10 bar CO 2 pressure . Similarly, efficient Al(III) and La(III) complexes were reported as Lewis acids for carbonation of limonene monoxide under mild conditions (70–85 °C, 10 bar CO 2 ). A different way to accelerate catalytic reactions is by means of organocatalytic hydrogen bond donors (HBDs) .…”

Effective and Reversible Carbon Dioxide Insertion into Cerium Pyrazolates

“…Thus, metalorganic derivatives easily react with or insert CO 2 , as initially demonstrated by Bochkarev et al for homoleptic silylamides Ln[N(SiMe 3 ) 2 ] 3 [7,8] and alkoxides [Ln(OnBu) 3 ] (Scheme 1 c,d). [9,10] Similar archetypes (including Ln III aryloxides) can also be used for chemical transformations, such as the catalytic conversion of a CO 2 /epoxide mixture into cyclic carbonates [11] or copolymers. [10a, 12, 13] However, highly reactive organo-rareearth-metal complexes such as alkyl [14] and hydride [10a, 15] (Scheme 1 a,b) or divalent derivatives [16] display irreversible CO 2 insertion or favor additional transformations through CO 2 post-activation (e.g.…”

Sustainable Heterogeneous Catalysts for CO2 Utilization by Using Dual Ligand ZnII/CdII Metal–Organic Frameworks

“…[25][26][27][28][29][30][31][32][33] For catalytic cycloaddition of CO 2 with epoxides to generate cyclic carbonates, av ariety of homogeneousc atalysts such as transition-metal complexes,i onic liquids, organocatalysts, and quaternary ammoniumo rp hosphonium salts, etc.,h ave been extensively studied, but catalyst recycling and product separation issues limit their practicality. [34][35][36][37][38][39][40][41][42][43][44][45][46][47] On the other hand, heterogeneous catalysts such as metal oxides, zeolites, and functionalp olymers have also been developed for the catalytic conversion of CO 2 ,w hicho ften entail high pressures of CO 2 and/orh igh activationt emperatures. [48][49][50][51][52][53][54][55][56][57][58][59] Thus, there is an unrelenting need to develop novel robust materials to absorb CO 2 and convert it into value-added chemicals through heterogeneous catalysis.…”