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Thiolate-Thione Redox-Active Ligand with a Six-Membered Chelate Ring via Template Condensation and Its Pt(II) Complexes. | LitMetric
A new template condensation reaction has been discovered in a mixture of Pt(II), thiobenzamide, and base. Four complexes of the general form [Pt(ctaPh)], R = CH (), H (), F ), Cl (), cta = ondensed hiomide, have been prepared under similar conditions and thoroughly characterized by H 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 with [CpCo] yielded [CpCo][Pt(ctaPh)], , which has been similarly characterized with the addition of EPR spectroscopy and SQUID magnetization. The singly reduced form containing , (nBuN)[Pt(ctaPh)], has been generated in situ and characterized by UV-vis and EPR spectroscopies. DFT studies of , , and 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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