From stoichiometry to catalysis: electroreductive coupling of alkynes and carbon dioxide with nickel-bipyridine complexes. Magnesium ions as the key for catalysis

Abstract

The incorporation of carbon dioxide into nonactivated alkynes catalyzed by elect regenerated nickel-bipyridinc complexes affords a,0-unsaturated acids in moderate to good yields. The electrocarboxylation reaction was undertaken on a preparative scale in the presence of a sacrificial magnesium anode: the formation of acids from alkynes is stoichiometric with respect to the nickel complex if performed in a two-compartment cell but can be made catalytic in a single-compartment cell. An intermediate nickelacycle was isolated from the reaction with 4-octyne. The cleavage of this metallacyde by magnesium ions is the key step to explain catalysis.

Utilization of Volatile Organic Compounds as an Alternative for Destructive Abatement

“…New interesting research area is the use of CO2 as a renewable and environmentally friendly source material of carbon in the hydrocarboxylation process. The promising results for CO2 process have been obtained with nickel and copper catalysts [241,243,244].…”

Umwandlung von Kohlendioxid mit Übergangsmetall‐Homogenkatalysatoren: eine molekulare Lösung für ein globales Problem?

“…[95] DuÇach et al wählten einen alternativen Zugang zu Nickel(0)-Katalysatoren für die Umsetzung von CO 2 mit Alkinen und Diinen. [96][97][98] [77,102,103] Auch andere Gruppen berichteten über die Produktaufarbeitung mit Säuren. [104][105][106][107][108][109] 4.…”

Electrocarboxylation of Alkynes with Carbon Dioxide in the Presence of Metal Salt Catalysts

“…In spite of the intrinsic thermodynamic stability of CO 2 , it can be readily reduced at the cathode 2 or indirectly activated by using transition metal complexes (Pd, Ni-, and Co). [3][4][5] In the last 50 years, many research groups have been devoted to study the fixation and conversion of CO 2 with various substrates involving alkenes, [6][7][8][9][10] alkynes, 5,[11][12][13] ketones, [14][15][16] halides, [17][18][19][20][21][22][23] epoxides [24][25] and imines. 26 The electrochemical fixation of CO 2 into the unsaturated hydrocarbons to form new carbon-carbon bonds is an interesting topic because it could afford valuable fine chemicals.…”