Synthesis and Structure of a Novel Substituted Benzothiazolyl-N-phenyl-2-pyridinecarbothioamide; Kinetics of Formation and Electrochemistry of Two of its Palladium Pincer Complexes

Mark A.W. Lawrence; Yvette A. Jackson; Willem H. Mulder; Per Martin Björemark; Mikael Håkansson

doi:10.1071/CH14380

RESEARCH ARTICLE

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Synthesis and Structure of a Novel Substituted Benzothiazolyl-N-phenyl-2-pyridinecarbothioamide; Kinetics of Formation and Electrochemistry of Two of its Palladium Pincer Complexes

Mark A.W. Lawrence ^A ^C , Yvette A. Jackson ^A , Willem H. Mulder ^A , Per Martin Björemark ^B and Mikael Håkansson ^B

+ Author Affiliations

- Author Affiliations

^A Department of Chemistry, University of the West Indies, Mona Campus, Kingston 7, Jamaica, West Indies.

^B Department of Chemistry and Molecular Biology, University of Gothenburg, Kemigården 4, Gothenburg, Sweden.

^C Corresponding author. Email: mark.lawrence02@uwimona.edu.jm

Australian Journal of Chemistry 68(5) 731-741 https://doi.org/10.1071/CH14380
Submitted: 12 June 2014 Accepted: 14 July 2014 Published: 14 October 2014

Abstract

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 Δ_fH = 8 ± 1 kJ mol^–1, Δ_fS^θ = 108 ± 10 J K^–1 mol^–1, and Δ_fH = 17 ± 4 kJ mol^–1 and Δ_fS^θ = 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.

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Synthesis and Structure of a Novel Substituted Benzothiazolyl-N-phenyl-2-pyridinecarbothioamide; Kinetics of Formation and Electrochemistry of Two of its Palladium Pincer Complexes

Abstract

References

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