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Updated: Feb 19, 2026

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Sulfur insertion into group 12 metal dithiolate complexes: metal-dependent equilibria
Muhammad Sohail1, Carsten Heinsen1, Allen G Oliver1
1Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana, USA. etsui@nd.edu.
Abstract:
Dianionic bis(carboxamide)pyridine-supported metal(II) dithiolate complexes of Cd2+ and Hg2+ showed isostructural [N3S2] coordination to a previously reported zinc variant, but changes in ionic radius resulted in distortion of the coordination geometries. While addition of elemental sulfur to the zinc dithiolate complex selectively inserts an "S3" unit to form a zinc tetrasulfanide complex, addition of S8 to the Cd2+ or Hg2+ congeners formed multiple products corresponding to sulfur insertion at both thiolate moieties, with different equilibrium constants of insertion. These reactions were correlated to comparisons of metal thiolate nucleophilicity and electrochemical oxidation potentials of the dithiolate complexes. These results point to additional contributions from ring strain and other structural/steric effects in controlling the thermodynamics of sulfur insertion.
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