Journalartikel

Investigations on the Reactivity of Copper(I) Complexes with a N3S Thioether Ligand System


AutorenlisteRotärmel, T; Specht, P; Becker, J; Neuba, A; Schindler, S

Jahr der Veröffentlichung2022

ZeitschriftEuropean Journal of Inorganic Chemistry

Bandnummer26

Heftnummer6

ISSN1434-1948

eISSN1099-0682

Open Access StatusHybrid

DOI Linkhttps://doi.org/10.1002/ejic.202200626

VerlagWiley-VCH Verlag


Abstract
In the active site of several copper monooxygenases, thioether residues are coordinated through the sulfur atom, e. g. dopamine-beta-monooxygenase (D beta M). The reaction of dioxygen with a series of copper(I) complexes with thioether groups in tripodal ligands based on either derivatives of tris(2-pyridylmethyl)amine (TMPA) or a guanidine system were investigated by low-temperature stopped-flow measurements. The formation of labile intermediates, an end-on superoxido complex, and mu-1,2-trans-peroxido copper(II) complexes were spectroscopically detected and a kinetic analysis allowed the calculation of activation parameters for these reactions supporting the postulated mechanism. Most interesting was the finding that replacing the ethyl group in the tren-guanidine derivative (Et-TMG)(2)(SEtEt)N with a methyl group allowed a dramatic increase in the stability of the formed superoxido copper complex. Measurements with ozone were performed in order to find an alternative way to obtain and stabilize the labile intermediates.



Zitierstile

Harvard-ZitierstilRotärmel, T., Specht, P., Becker, J., Neuba, A. and Schindler, S. (2022) Investigations on the Reactivity of Copper(I) Complexes with a N3S Thioether Ligand System, European Journal of Inorganic Chemistry, 26(6), Article e202200626. https://doi.org/10.1002/ejic.202200626

APA-ZitierstilRotärmel, T., Specht, P., Becker, J., Neuba, A., & Schindler, S. (2022). Investigations on the Reactivity of Copper(I) Complexes with a N3S Thioether Ligand System. European Journal of Inorganic Chemistry. 26(6), Article e202200626. https://doi.org/10.1002/ejic.202200626



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