The effects of chelating N₄ ligand coordination on Co(ii)-catalysed photochemical conversion of CO₂ to CO: reaction mechanism and DFT calculations

Abstract

cis-[Co(PDP)Cl2] complex mediated reduction conversion of CO2 to CO under photocatalytic or electrocatalytic conditions with high turnovers or Faraday efficiency.

CoIICryptates Convert CO2into CO and CH4under Visible Light

“…Apart from cryptates, cyclams and their derivatives, [6,10,35] porphyrins and somea nalogues, [12,13,36,37] polypyridyl [23,38,39] and other [30,33,[40][41][42][43] ligandsh ave been associated with cobalt to photoreduceC O 2 .F or instance, Tinnemans et al [10] used Co II and Co III complexes bearing diamine macrocyclic ligands as catalysts, with [Ru(bipy) 3 ] 2 + as PS and ascorbic acid as SED, leadingt ot he observation of CO and H 2 with al ow CO selectivity of < 35 %a nd turnover number (TON) values below 350.…”

Synthesis and phosphatase activity of a Cobalt(II) phenanthroline complex

“…5,6 Cobalt(II) complexes are interesting for their capability to bind dioxygen reversibly [7][8][9] and for their catalytic * For correspondence Electronic supplementary material: The online version of this article (doi:10.1007/s12039-017-1355-6) contains supplementary material, which is available to authorized users. applicability in different oxidation reactions, [10][11][12][13] in particular for the oxidation of phenols, alcohols, flavonoides, nitroalkanes, hydrazines or olefins. [14][15][16] In addition, cobalt complexes have gained importance because of their application as potential hypoxia-activated prodrugs.…”

Artificial Photosynthetic Systems for CO2 Reduction: Progress on Higher Efficiency with Cobalt Complexes as Catalysts

“…[32] This hybrid photocatalyst showed enhanced activity towardsC O 2 reduction in comparison to bare GO or ap hysical Scheme4.Proposed mechanism of Che's work (L = ligand of C15). [28] ChemSusChem 2017, 10,4393 -4402 www.chemsuschem.org mixture of GO and C23 in the presence of TEA as SED in water. Underv isible light irradiation, methanol was produced as the main product from the system with ap roduction rate of 78.8 mmol g À1 h…”

“…[29] In 2016, Che and co-workers reported as eries of novel cis-[Co(N 4 )Cl 2 ]c omplexes (C15-C18;F igure 3) for CO 2 reduction. [28] These complexes adopt octahedral cis-coordinationg eometry in the solid state with two chloride ligandsa tcis positions. They found the activity towards CO 2 reduction of the cobalt catalysts in either photocatalytic or electrocatalytic system was highly affectedb yt he N 4 ligand structure.…”

“…[14][15][16][17][18][19][20][21][22][23][24] These systems realized CO 2 -to-CO and/or CO 2 -to-formate conversion successfully under light irradiation. Recently,awidev ariety of novel cobaltc omplexes have been reported for photocatalytic CO 2 reduction, [25][26][27][28][29][30][31] exhibitingi mpressive activitiesa nd selectivities. Moreover,s omep reviously reportedm olecular cobalt catalysts have also been used to fabricate hybridc atalysts or photoelectrodes for heterogeneous photocatalytic or photoelectrochemicalCO 2 reduction.…”