Synthesis and Structure of a Novel Substituted Benzothiazolyl-N-phenyl-2-pyridinecarbothioamide; Kinetics of Formation and Electrochemistry of Two of its Palladium Pincer Complexes
The synthesis and crystal structures of bis-N-(2,5-dimethoxyphenyl)pyridine-2,6-dicarbothioamide (dicarbothioamide I) and 6-(4,7-dimethoxy-2-benzothiazolyl)-N-(2,5-dimethoxyphenyl)-2-pyridinecarbothioamide (L1) as well as the syntheses of the palladium(ii) chloride and acetate pincer complexes are reported. The stability constant for the palladium complex formation at 25°C was found to be (2.04 ± 0.26) × 104 dm3 mol–1 and (2.30 ± 0.19) × 104 dm3 mol–1 with ΔfH = 8 ± 1 kJ mol–1, ΔfSθ = 108 ± 10 J K–1 mol–1, and ΔfH = 17 ± 4 kJ mol–1 and ΔfSθ = 140 ± 20 J K–1 mol–1 for the PdClL1 and Pd(OAc)L1, respectively. The kinetics of formation of the palladium(ii) complexes were investigated and the mechanism is proposed to be associative in nature (ΔH1‡ = 34 ± 2 kJ mol–1 and ΔS1‡ = –113 ± 8 J K–1 mol–1, and ΔH1‡ = 37 ± 3 kJ mol–1 and ΔS1‡ = –100 ± 8 J K–1 mol–1 for the PdClL1 and Pd(OAc)L1 species, respectively). The electrochemical measurements of the acetonitrile solutions revealed irreversible electron transfers consistent with the electrochemical decomposition of the ligand and its coordination complexes.