Calix[4]pyrrolato gallate: square planar-coordinated gallium(iii) and its metal-ligand cooperative reactivity with CO2 and alcohols.
Chem Sci
; 13(37): 11215-11220, 2022 Sep 28.
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| ID: mdl-36320463
ABSTRACT
Forcing a priori tetracoordinate atoms into planar configuration represents a promising concept for enhanced reactivity of p-block element-based systems. Herein, the synthesis, characterization, and reactivity of calix[4]pyrrolato gallates, constituting square planar-coordinated gallium(iii) atoms, are reported. Unusual structural constraint-induced Lewis acidity against neutral and anionic donors is disclosed by experiment and rationalized by computations. An energetically balanced dearomatization/rearomatization of a pyrrole unit enables fully reversible metal-ligand cooperative capture of CO2. While alcohols are found unreactive against the gallates, a rapid and selective OH-bond activation can be triggered upon protonation of the ligand. Secondary ligand-sphere modification adds a new avenue to structurally-constrained complexes that unites functional group tolerance with unconventional reactivity.
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Chem Sci
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2022
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Article