Terpyridine complexes of first row transition metals and electrochemical reduction of CO₂ to CO

Abstract

Homoleptic terpyridine complexes of first row transition metals are evaluated as catalysts for the electrocatalytic reduction of CO2. Ni and Co-based catalytic systems are shown to reduce CO2 to CO under the conditions tested. The Ni complex was found to exhibit selectivity for CO2 over proton reduction while the Co-based system generates mixtures of CO and H2 with CO : H2 ratios being tuneable through variation of the applied potential.

Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

“…This is due to an antiferromagnetic coupling of the Ni(I), and the tpy •− radical and the calculations are in agreement with magnetic data [41]. [40,41,52,[90][91][92][93]. A recent study revealed that this sequence is true for six coordinated [Ni(tpy) 2 ] n complexes [41].…”

“…The complex [Ni(II)(tpy)2] 2+ is reversibly reduced in three one-electron steps, and can also be reversibly oxidized (Scheme 15) [40,41,52,[90][91][92][93]. For the oxidized species a [Ni(III)(tpy)2] 3+ character has recently been assumed from calculations [41]; however, further spectroscopic evidence is not available from this report.…”

“…The authors ascribed this to the high reactivity of [Ni(III)(tpy)3] 3+ in air, decomposing the isolated compound upon workup and isolation. [40,41,52,[90][91][92][93]. A recent study revealed that this sequence is true for six coordinated [Ni(tpy)2] n complexes [41].…”

Efficient and selective molecular catalyst for the CO 2 -to-CO electrochemical conversion in water

“…The problem should, however, resurface upon going to stronger acids. That competition with hydrogen evolution is a general issue for molecular catalysis of the CO 2 -to-CO conversion is confirmed by recent findings concerning catalysts derived from terpyridine complexes of first-row transition metals in (90:10, vol:vol) DMF/H 2 O mixtures (28).…”

Coordination complexes and biomolecules: A wise wedding for catalysis upgrade

“…Such mimics (structural, functional or both) were thus developed for hydrogenases [1][2][3][4], superoxide dismutases [5][6][7][8][9], photosynthetic system [10,11], oxygenases [12] etc. These systems go from the simplest, using very usual metallic ions and ligands [13] to the most sophisticated ones [14][15][16]. Even though models of metalloenzymes are very helpful for investigation purposes, these models are often poor catalysts (with respect to their loadings).…”