A1 Journal article (refereed)
Reaction mechanism of regioisomerization in binuclear (diaminocarbene)PdII complexes (2021)

Mikherdov, A. S., Popov, R. A., Kinzhalov, M. A., Haukka, M., Polukeev, V. A., Boyarskiy, V. P., & Roodt, A. (2021). Reaction mechanism of regioisomerization in binuclear (diaminocarbene)PdII complexes. Inorganica Chimica Acta, 514, Article 120012. https://doi.org/10.1016/j.ica.2020.120012

JYU authors or editors

Publication details

All authors or editors: Mikherdov, Alexander S.; Popov, Roman A.; Kinzhalov, Mikhail A.; Haukka, Matti; Polukeev, Valeriy A.; Boyarskiy, Vadim P.; Roodt, Andreas

Journal or series: Inorganica Chimica Acta

ISSN: 0020-1693

eISSN: 1873-3255

Publication year: 2021

Volume: 514

Article number: 120012

Publisher: Elsevier

Publication country: Netherlands

Publication language: English

DOI: https://doi.org/10.1016/j.ica.2020.120012

Publication open access: Not open

Publication channel open access:

Abstract

A series of binuclear PdII carbene complexes were synthesized via the treatment of cis-[PdCl2(CNXyl)2] (1) with benzo-1,3-thiazol-2-amines (2–6) and structurally characterized. In every case the reaction leads to the mixture of two regioisomers, which are able to interconvert. The study of the regioisomerization of the binuclear diaminocarbene species showed that it is a first-order reaction, that is, it occurs intramolecularly, and was analyzed with the Hammett function. Electron-withdrawing substituents in the benzothiazole moiety of the complexes as well as increasing the solvent polarity accelerate the reaction. The solvent donor strength correlates less well with the isomerization rates. Based on the obtained activation parameters the studied regioisomerization could be defined as the interchange/dissociative process type. A combined approach including kinetic and mass spectrometric studies allowed the conclusion that the rate-determining step of the isomerization is breaking the carbon–nitrogen bond in the carbene fragment of the binuclear complex.

Keywords: coordination complexes; palladium; chemical synthesis; reaction mechanisms; isomerism

Free keywords: (diaminocarbene)PdII complexes; regioisomerization; kinetics; benzothiazol-2-amines; Hammett correlation

Contributing organizations

Ministry reporting: Yes

Reporting Year: 2021

JUFO rating: 1