Carbonate Templated Self-Assembly of an Alkylthiolate Bridged Cadmium Macrocycle

摘要

In the presence of Cd (ClO4)2 and base, a new mixed N,S-donor alkylthiolate ligand supported both carbonate formation from atmospheric CO2 and self-assembly of a novel bis-capped puckered (CdS)6 molecular wheel with 3-fold symmetry. The remarkable stability of the complex was demonstrated by slow intermolecular ligand exchange on the ²J(HH) and J(^111/113Cd¹H) time scales at elevated temperature. Both CO2 and base were required to convert amorphous “Cd>LClO4” precipitated in the absence of air to the carbonate complex. The complex shares structural features with the ζ-carbonic anhydrase class associating Cd(II) with the biogeochemical cycling of carbon and is the first structurally characterized carbonate complex of any metal involving an alkylthiolate ligand.