Reaction mechanism of regioisomerization in binuclear (diaminocarbene)PdII complexes
Publiceringsår
2021
Upphovspersoner
Mikherdov, Alexander S.; Popov, Roman A.; Kinzhalov, Mikhail A.; Haukka, Matti; Polukeev, Valeriy A.; Boyarskiy, Vadim P.; Roodt, Andreas
Abstrakt
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.
Visa merOrganisationer och upphovspersoner
Jyväskylä universitet
Haukka Matti
Publikationstyp
Publikationsform
Artikel
Moderpublikationens typ
Tidning
Artikelstyp
En originalartikel
Målgrupp
VetenskapligKollegialt utvärderad
Kollegialt utvärderadUKM:s publikationstyp
A1 Originalartikel i en vetenskaplig tidskriftPublikationskanalens uppgifter
Journal
Förläggare
Volym
514
Artikelnummer
120012
ISSN
Publikationsforum
Publikationsforumsnivå
1
Öppen tillgång
Öppen tillgänglighet i förläggarens tjänst
Nej
Parallellsparad
Nej
Övriga uppgifter
Vetenskapsområden
Kemi
Nyckelord
[object Object],[object Object],[object Object],[object Object],[object Object]
Publiceringsland
Nederländerna
Förlagets internationalitet
Internationell
Språk
engelska
Internationell sampublikation
Ja
Sampublikation med ett företag
Nej
DOI
10.1016/j.ica.2020.120012
Publikationen ingår i undervisnings- och kulturministeriets datainsamling
Ja