Transition metal mediated coupling of carbon dioxide and ethene to acrylic acid/acrylates

Insights into the Base‐Assisted Acrylate Formation from CO2/C2H4 Coupling by Pd‐ and Ni‐catalyst: A DFT Mechanistic Study

“…Most importantly, the final product η 2 ‐C,C‐coordinated acrylate complex 6 Ni lay below the reference point 2 Ni , demonstrating the acrylate synthesis reaction became exergonic with the addition of bases. As we concluded in our former work and in other references, the synthesis of acrylic acid from CO 2 and C 2 H 4 is hard to occur given to its endergonic nature ,. While by adding external bases, the formation of acrylate from CO 2 /C 2 H 4 in turn became thermodynamically applicable, just as announced in previous reports ,.…”

Liberation of acrylates from nickelalactones via Ni─O ring opening with alkyl iodides

“…The transformation of carbon dioxide into high‐added‐value chemicals is attractive for the chemical industry . Carbon dioxide may be converted into bulk chemicals such as formate and acrylates .…”

“…The transformation of carbon dioxide into high-added-value chemicals is attractive for the chemical industry. [1][2][3] Carbon dioxide may be converted into bulk chemicals such as formate and acrylates. [4][5][6][7][8] However, CO 2 is a thermodynamically and kinetically stable molecule, rendering its transformation particularly difficult.…”

The coupling of carbon dioxide with ethene to produce acrylic acid sodium salt in one pot by using Ni(II) and Pd(II)-phosphine complexes as precatalysts

“…The most used route to form such species is the in situ synthesis from Ni(0) complexes, such as Ni(COD) 2 , Ni(PPh 3 ) 4 , etc., and the suitable ligands. As the Ni(0) sources would be difficult to handle and manipulate because of their high air sensitivity and thermal instability, in some papers the more stable Ni(II) complexes are used as pre-catalysts, which are then reduced in situ to zerovalent nickel usually by treatment with external reductants, for instance by addition of zinc dust [13][14][15][16][17]47]. Also the Pd(0) complexes catalyze the title reaction but they activity is usually lower than by using Ni(0) precursors.…”

“…Nevertheless, from an industrial point of view, it is still considered as a viable alternative option to some traditional processes in particular when the target products are value-added, economical and in demand [9][10][11][12][13][14][15]. As a matter of fact, the industrial utilization of CO 2 is presently limited to the production of bulk chemicals like salicylic acid, urea, cyclic carbonates and polypropylene carbonate [7][8][9][10]15], even if one of the most interesting challenge for the industry is represented by the CO 2 coupling with olefins to produce acrylate [16][17][18][19][20][21][22][23][24][25][26]. This process would be sustainable and economical, as applications of acrylates are ubiquitous, particularly in the field of coatings, adhesives, construction chemicals, hygiene products and paints.…”