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 “CdLClO4” 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.
The versatile pyridyl synthons of mixed N,Se donor ligands bis(pyridin-2-ylmethyl)selane (L) and 1,2bis(pyridin-2-ylmethyl)diselane (L*) served the dual roles of metal chelating anchors and mediators of supramolecular associations in a crystallographic approach to documenting uncommon bonding between divalent Group 12 metal ions and neutral selenium functionalities. Five new molecular species with diverse ligand configurations and conformations were structurally characterized. Two macrocyclic polymorphs of [ZnLCl 2 ] have intermolecular Se−Cl interactions rather than the desired intramolecular Zn−Se binding. Rare examples of Cd(II)-selenoether bonding are provided by tricoordinate L in dinuclear [CdLCl(μ-Cl)] 2 and mononuclear [CdL(μ-NO 3 ) 2 ]. Unique intramolecular Zn-selenoether and Cd-diselenide bonds are reported for [ZnL(μ-NO 3 ) 2 ] and [CdL*(μ-NO 3 ) 2 ], respectively. In addition, a cocrystal of [CdL(μ-NO 3 ) 2 ] and [CdL*(μ-NO 3 ) 2 ] is structurally characterized. The intermolecular pyridyl π-interactions observed in these diverse structures are highlighted.
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