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The rate of substitution from η6-arene ruthenium(II) complexes

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Abstract

The rate and mechanism of substitution in the Ru(II) complexes (C1–C6) by thiourea nucleophiles was studied at pH 2 and rate constants measured as a function of nucleophile concentrations and temperature using spectrometric methods. There is increased electron density at the Ru metal atom of C2 as a result of inductive donation by substituents on the arene ligand, making it less positive and therefore less reactive than C1. For the complexes C3–C6 bearing the 2,2′-bipyridyl ligand, the aqua ligands are located trans to the arene ligands, and hence, their reactivity increases in accordance to the number and type of alkyl substituents on the η6-arene ligands which donate inductively into the π-molecular orbitals, causing increased trans labialisation of the coordinated aquo co-ligand. Compared to the reactivity of triaquo complex (C1), the auxiliary bipyridyl ligand of (C3) complex lowers the rate of substitution for the later complex by a factor of about 100, possibly due to its steric hindrance at the Ru(II) metal centre. The significantly negative activation entropies and positive activation enthalpies suggest an associative mode of substitution. The reactivity of the nucleophiles follow the order DMTU > TU > TMTU.

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Acknowledgements

The authors greatly acknowledge the financial support from the University of KwaZulu-Natal, South Africa. We also thank Mr Craig Grimmer for his support with NMR measurements and Mrs Caryl Janse Van Rensburg for her help with mass spectra and elemental analyses.

Funding

Funding was provided by South African Agency for Science and Technology Advancement and University of KwaZulu-Natal (Inyuvesi Yakwazulu-Natali).

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  1. School of Chemistry and Physics, University of KwaZulu-Natal, Private Bag X01, Scottsville, Pietermaritzburg, 3209, South Africa

    Meshack K. Sitati & Allen Mambanda

  2. School of Science, College of Science and Technology, University of Rwanda, P.O. Box 4285, Kigali, Rwanda

    Deogratius Jaganyi

  3. Department of Chemistry, Faculty of Applied Sciences, Durban University of Technology, P.O. Box 1334, Durban, 4000, South Africa

    Deogratius Jaganyi

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  1. Meshack K. Sitati
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Sitati, M.K., Jaganyi, D. & Mambanda, A. The rate of substitution from η6-arene ruthenium(II) complexes. Transit Met Chem 45, 305–315 (2020). https://doi.org/10.1007/s11243-020-00380-1

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