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RESEARCH ARTICLE
Contents Vol 77(7)

Synthesis, characterization and base hydrolysis of cobalt(III) complexes coordinated by substituted phenylthioether ligands

Lee Roecker https://orcid.org/0000-0001-8809-4635 A B * , Alicia Cohn B , Thomas Cox B , Rachel Ceaglske A , Olivia Rick A , Ella Miller Knagge A and Sean Parkin https://orcid.org/0000-0001-5777-3918 C *
+ Author Affiliations
- Author Affiliations

A Department of Chemistry, Northern Michigan University, Marquette, MI 49855, USA.

B Department of Chemistry, Gettysburg College, Gettysburg, PA 17325, USA.

C Department of Chemistry, University of Kentucky, Lexington, KY 40506, USA.

* Correspondence to: lroecker@nmu.edu, s.parkin@uky.edu

Handling Editor: Martyn Coles

Australian Journal of Chemistry 77, CH24012 https://doi.org/10.1071/CH24012
Submitted: 31 January 2024  Accepted: 1 July 2024  Published online: 17 July 2024

© 2024 The Author(s) (or their employer(s)). Published by CSIRO Publishing.

Abstract

A synthetic route to the preparation of cobalt(III) complexes coordinated by bidentate phenylthioether ligands is described. Complexes of the type ((2-(X-phenylthio)ethylamine)-N,S)bis(ethylenediamine)cobalt(III) perchlorate, [(en)2Co(S(X-phenyl)CH2CH2NH2)](ClO4)3, where X = 4-methoxy (2a), 4-methyl (2b), 3-methyl (2c), nothing (2d), 3-methoxy (2e), 4-bromo (2f) and 3-bromo (2g) were prepared. The synthetic route involves reaction of trans-dichloridobis(ethylenediamine)cobalt(III) chloride with NH2CH2CH2SC6H4X to produce cis-[(en)2CoCl(NH2CH2CH2SC6H4X)]Cl2 (1a–g). Formation of the Co–S bond, completing the ring closure, is then accomplished by removing the coordinated chlorido by addition of AgClO4 in sulfolane. Complexes were characterized by 1H and 13C NMR spectroscopy, UV-Vis spectroscopy and elemental analysis. In addition, the solid-state structure (X-ray) of the monohydrate of 2d confirms the coordination mode of the ligand. Preliminary kinetic investigations in basic solution show that the Co–S bond is broken resulting in the formation of [(en)2Co(OH)(NH2CH2CH2SC6H4X)]2+. At 15.0°C, a Hammett Plot is linear (r2 = 0.981) with ρ = 2.24 ± 0.13.

Keywords: base hydrolysis, cobalt(III), coordination chemistry, Hammett Plot, reaction mechanisms, SN1CB, thioether, X-ray structure.

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