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Australian Journal of Chemistry Australian Journal of Chemistry Society
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RESEARCH ARTICLE

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 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.


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