Cooperativity in Shape-Persistent Bis-(Zn-salphen) Catalysts for Efficient Cyclic Carbonate Synthesis under Mild Conditions

Abstract

A series of conformationally rigid (Zn-salphen)2 complexes with a planar bridging component (xanthene or dibenzofuran) are described. Conformational changes for these assemblies are essentially limited to the axial rotation of the Zn-salphen moieties; however, such geometric constraints crucially permit the subtle tuning of the intermetallic separation and geometry to potentially enhance catalytic activity (and cooperative effects). The complexes have been investigated as catalysts in conjunction with n Bu4NI for the coupling of CO2 with epoxides. Selected dibenzofuran derivatives are significantly more active for the production of cyclic carbonate than their mononuclear analogues under identical conditions and concentrations of Zn sites. High initial turnover frequencies (up to 29 000 h–1; 14 500 h–1 per Zn, using 10 bar of CO2 at 95 °C) and excellent efficiencies under mild conditions (1 bar of CO2 at 55 °C) have been achieved. Kinetic studies using in situ (ReactIR) spectroscopy and density functional theory calculations have been performed, which reveal the existence of an intramolecular rate component and a preference for the cooperative pathway as well as transition states that depict the Zn sites operating in tandem. Taken together, these results provide strong evidence of cooperative reactivity in these Zn2 catalysts.

Recent progress in CO2 conversion into organic chemicals by molecular catalysis

“…The conformational rigid (Zn-salphen) 2 complex CAT-10 with a planar bridging component (dibenzofuran) are described as catalysts in conjunction with TBAI for the coupling of CO 2 with epoxides. 66 The geometric constraints permit the subtle tuning of the intermetallic separation and geometry to potentially enhance the catalytic activity. As a result, high initial turnover frequencies and excellent efficiencies under mild conditions are achieved (entries 14 and 15).…”