Reaction mechanism of regioisomerization in binuclear (diaminocarbene)PdII complexes

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Reaction mechanism of regioisomerization in binuclear (diaminocarbene)PdII complexes. / Михердов, Александр Сергеевич; Попов, Роман Александрович ; Кинжалов, Михаил Андреевич; Хаукка, Матти; Полукеев, В.А.; Боярский, Вадим Павлович; Руудт, Андреас.

в: Inorganica Chimica Acta, Том 514, 120012, 01.01.2021.

Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование

BibTeX

@article{13b08636bb0a4aefa26c87951b36eb28,

title = "Reaction mechanism of regioisomerization in binuclear (diaminocarbene)PdII complexes",

abstract = "A series of binuclear Pd II carbene complexes were synthesized via the treatment of cis-[PdCl 2(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 = "(Diaminocarbene)Pd complexes, Benzothiazol-2-amines, Hammett correlation, Kinetics, Regioisomerization, (Diaminocarbene)PdII complexes, (Diaminocarbene)Pd-II complexes, ISONITRILES, N-HETEROCYCLIC CARBENES, ISOCYANIDE COMPLEXES, X-RAY, DIFFRACTION, ACYCLIC DIAMINOCARBENES, LIGAND, BOND, CATALYSTS, METAL-COMPLEXES",

author = "Михердов, {Александр Сергеевич} and Попов, {Роман Александрович} and Кинжалов, {Михаил Андреевич} and Матти Хаукка and В.А. Полукеев and Боярский, {Вадим Павлович} and Андреас Руудт",

note = "Publisher Copyright: {\textcopyright} 2020 Elsevier B.V.",

year = "2021",

month = jan,

day = "1",

doi = "10.1016/j.ica.2020.120012",

language = "English",

volume = "514",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier",

}

RIS

TY - JOUR

T1 - Reaction mechanism of regioisomerization in binuclear (diaminocarbene)PdII complexes

AU - Михердов, Александр Сергеевич

AU - Попов, Роман Александрович

AU - Кинжалов, Михаил Андреевич

AU - Хаукка, Матти

AU - Полукеев, В.А.

AU - Боярский, Вадим Павлович

AU - Руудт, Андреас

PY - 2021/1/1

Y1 - 2021/1/1

N2 - A series of binuclear Pd II carbene complexes were synthesized via the treatment of cis-[PdCl 2(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.

AB - A series of binuclear Pd II carbene complexes were synthesized via the treatment of cis-[PdCl 2(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.

KW - (Diaminocarbene)Pd complexes

KW - Benzothiazol-2-amines

KW - Hammett correlation

KW - Kinetics

KW - Regioisomerization

KW - (Diaminocarbene)PdII complexes

KW - (Diaminocarbene)Pd-II complexes

KW - ISONITRILES

KW - N-HETEROCYCLIC CARBENES

KW - ISOCYANIDE COMPLEXES

KW - X-RAY

KW - DIFFRACTION

KW - ACYCLIC DIAMINOCARBENES

KW - LIGAND

KW - BOND

KW - CATALYSTS

KW - METAL-COMPLEXES

UR - http://www.scopus.com/inward/record.url?scp=85092214365&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/99f45eea-23ac-30dd-90b2-637787c95ced/

U2 - 10.1016/j.ica.2020.120012

DO - 10.1016/j.ica.2020.120012

M3 - Article

VL - 514

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

M1 - 120012

ER -

ID: 62252733

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