Carbonate-Templated Self-Assembly of an Alkylthiolate-Bridged Cadmium Macrocycle

In the presence of Cd­(ClO4)2 and a base, a new mixed N,S-donor alkylthiolate ligand supported both carbonate formation from atmospheric CO2 and the self-assembly of a novel bicapped puckered (CdS)6 molecular wheel. 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 the base were required to convert amorphous “CdLClO4” precipitated in the absence of air to the carbonate complex. The complex shares structural features with the ζ-carbonic anhydrase class associating cadmium­(II) with the biogeochemical cycling of carbon and is the first structurally characterized carbonate complex of any metal involving an alkylthiolate ligand.