A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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-tekijät tai -toimittajat

Julkaisun tiedot

Julkaisun kaikki tekijät tai toimittajat: Mikherdov, Alexander S.; Popov, Roman A.; Kinzhalov, Mikhail A.; Haukka, Matti; Polukeev, Valeriy A.; Boyarskiy, Vadim P.; Roodt, Andreas

Lehti tai sarja: Inorganica Chimica Acta

ISSN: 0020-1693

eISSN: 1873-3255

Julkaisuvuosi: 2021

Volyymi: 514

Artikkelinumero: 120012

Kustantaja: Elsevier

Julkaisumaa: Alankomaat

Julkaisun kieli: englanti

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

Julkaisun avoin saatavuus: Ei avoin

Julkaisukanavan avoin saatavuus: 

Tiivistelmä

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.

YSO-asiasanat: kompleksiyhdisteet; palladium; kemiallinen synteesi; reaktiomekanismit; isomeria

Vapaat asiasanat: (diaminocarbene)PdII complexes; regioisomerization; kinetics; benzothiazol-2-amines; Hammett correlation

Liittyvät organisaatiot

OKM-raportointi: Kyllä

Raportointivuosi: 2021

JUFO-taso: 1