Copolymerization of Carbon Dioxide with Epoxides Catalyzed by Structurally Well-Characterized Dinickel Bis(benzotriazole iminophenolate) Complexes: Influence of Carboxylate Ligands on the Catalytic Performance

Inorganic Chemistry
Li-Shin HuangBao-Tsan Ko

Abstract

A series of structurally well-defined dinickel carboxylate complexes based on theRBiIBTP derivatives [RBiIBTP = bis(benzotriazole iminophenolate), where R = 3C for the propyl-bridged backbone and 5C for the 2,2-dimethyl-1,3-propyl-bridged backbone] were synthesized and developed for copolymerization of CO2and epoxides. The one-pot reactions of nickel perchlorate with theRBiIBTP-H2proligands and an appropriate amount of carboxylic acid derivatives (CF3COOH or 4-X-C6H4CO2H; X = H, CF3, OMe) upon the addition of triethylamine in refluxing methanol (MeOH) afforded dinuclear nickel dicarboxylate complexes, which could be formulated as either [(RBiIBTP)Ni2(O2CCF3)2] (1 and 2) or [(RBiIBTP)Ni2(O2CC6H4-4-X)2] (3-7). The dinickel monobenzoate complexes [(RBiIBTP)Ni2(O2CPh)(ClO4)(H2O)] [R = 3C (8) and 5C (9)] were prepared by using a similar synthetic route in tetrahydrofuran under reflux with a ligand precursor to metal salt to benzoic acid ratio of 1:2:1 in the presence of NEt3. Recrystallization of neutral nickel perchlorate complex 8 in a saturated MeOH or ethanol (EtOH) solution gave ionic and alcohol-solvated monobenzoate bimetallic analogues [(3CBiIBTP)Ni2(O2CPh)(S)2]ClO4, where S = MeOH (10) and EtOH (11). Single-crystal X-ray cr...Continue Reading

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Citations

Jun 6, 2019·Chemical Communications : Chem Comm·Ralte LalrempuiaErwan Le Roux
Jul 6, 2019·Chemical Society Reviews·Bruno GrignardChristophe Detrembleur
Nov 27, 2019·ChemSusChem·Jin HuangOlivier Coulembier

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