Water soluble bifunctional complex of tetrapyridino porphyrazinato zinc(II) as highly efficient catalyst for CO2 insertion into epoxide cycles

Metal–Cocatalyst Interaction Governs the Catalytic Activity of MII-Porphyrazines for Chemical Fixation of CO2

“…The absence of catalytic activity of 1 in the presence of chloride ions indicates that the equilibrium must be shifted mainly to the formation of inert species, in a way that cyclic carbonate formation is catalyzed exclusively by the free Cl – ions in solution, as in the control experiments. Such inert species have already been reported for bifunctional Zn II -tetrazaporphyrins, when DMSO and acetonitrile acted as axial ligands …”

“…To test this hypothesis, we synthesized six Pz complexes ( 1 – 6 ) containing different metal ions or substituents with variable electron-withdrawing abilities, as represented in Scheme . To the best of our knowledge, there is only one work in the literature reporting Pzs in the chemical fixation of CO 2 so far, which investigates a cationic Zn II tetrapyridino porphyrazine as a bifunctional catalyst . Pyridino Pzs consists of pyridine groups fused to the central ring, which makes substituents attached to this portion even farther from the core.…”

Novel hydroxyl-functionalized ionic liquids as efficient catalysts for the conversion of CO2 into cyclic carbonates under metal/halogen/cocatalyst/solvent-free conditions

“…[4][5][6][7] One of the most effective methods is to convert carbon dioxide and epoxides into the corresponding cyclic carbonates, because this reaction can not only achieve 100% atom utilization but also the resulting cyclic carbonates can be used as important chemical intermediates to synthesize specialty fine chemicals. [8][9][10][11][12][13] Various heterogeneous and homogeneous catalysts, including metal oxides, 14,15 molecular sieves, [16][17][18][19][20] transition metal complexes, [21][22][23][24][25] alkali metal salts, 26,27 quaternary ammonium salts, [28][29][30] metal-organic frameworks, [31][32][33][34][35] Lewis acids or bases, [36][37][38] and various ionic liquids, [39][40][41][42][43][44][45][46][47][48][49] have been utilized to catalyze cycloaddition reactions. However, mo...…”

Elucidating the role of non-covalent interactions in unexpectedly high and selective CO2 uptake and catalytic conversion of porphyrin-based ionic organic polymers

“…53 In addition to their multiple CO2-philic functional sides, both viologen and porphyrin are also known to exhibit effective CO2 catalytic conversion, which makes them very promising bifunctional materials in CCU applications. [46][47][48][54][55][56] Herein, based on the above considerations, we report viologen-linked porphyrin ICOPs (H2-ICOP and Zn-ICOP) synthesized through the Zincke reaction of H2 and Zn(II) tetrakis (4-aminophenyl) porphyrin with viologen Zincke salt, as presented in Scheme 1.…”