Reaction mechanism of regioisomerization in binuclear (diaminocarbene)PdII complexes
Year of publication
2021
Authors
Mikherdov, Alexander S.; Popov, Roman A.; Kinzhalov, Mikhail A.; Haukka, Matti; Polukeev, Valeriy A.; Boyarskiy, Vadim P.; Roodt, Andreas
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.
Show moreOrganizations and authors
University of Jyväskylä
Haukka Matti
Publication type
Publication format
Article
Parent publication type
Journal
Article type
Original article
Audience
ScientificPeer-reviewed
Peer-ReviewedMINEDU's publication type classification code
A1 Journal article (refereed), original researchPublication channel information
Journal
Publisher
Volume
514
Article number
120012
ISSN
Publication forum
Publication forum level
1
Open access
Open access in the publisher’s service
No
Self-archived
No
Other information
Fields of science
Chemical sciences
Keywords
[object Object],[object Object],[object Object],[object Object],[object Object]
Publication country
Netherlands
Internationality of the publisher
International
Language
English
International co-publication
Yes
Co-publication with a company
No
DOI
10.1016/j.ica.2020.120012
The publication is included in the Ministry of Education and Culture’s Publication data collection
Yes