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Updated: Oct 24, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Thiolate-Thione Redox-Active Ligand with a Six-Membered Chelate Ring via Template Condensation and Its Pt(II)
Linda A Zuckerman1, Natasha P Vargo2, Claire V May1
1Department of Chemistry, Boston University, Boston, Massachusetts 02215, United States.
Abstract:
A new template condensation reaction has been discovered in a mixture of Pt(II), thiobenzamide, and base. Four complexes of the general form [Pt(ctaPhR)2], R = CH3 (1a), H (1b), F (1c), Cl (1d), cta = condensed thioamide, have been prepared under similar conditions and thoroughly characterized by 1H NMR and UV-vis-NIR spectroscopy, (spectro)electrochemistry, elemental analysis, and single-crystal X-ray diffraction. The ligand is redox active and can be reduced from the initial monoanion to a dianionic and then trianionic state. Chemical reduction of 1a with [Cp2Co] yielded [Cp2Co]2[Pt(ctaPhCH3)2], [CpCo][1a], which has been similarly characterized with the addition of EPR spectroscopy and SQUID magnetization. The singly reduced form containing [1a], (nBu4N)[Pt(ctaPhCH3)2], has been generated in situ and characterized by UV-vis and EPR spectroscopies. DFT studies of 1b, [1b], and [1b] confirm the location of additional electrons in exclusively ligand-based orbitals. A detailed analysis of this redox-active ligand, with emphasis on the characteristics that favor noninnocent behavior in six-membered chelate rings, is included.
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