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Reaction between indazole and Pd-bound isocyanides—A theoretical mechanistic study. / Casella, Girolamo; Casarin, Maurizio; Kukushkin, Vadim Yu; Kuznetsov, Maxim L.

в: Molecules, Том 23, № 11, 2942, 10.11.2018.

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

Harvard

Casella, G, Casarin, M, Kukushkin, VY & Kuznetsov, ML 2018, 'Reaction between indazole and Pd-bound isocyanides—A theoretical mechanistic study', Molecules, Том. 23, № 11, 2942. https://doi.org/10.3390/molecules23112942

APA

Casella, G., Casarin, M., Kukushkin, V. Y., & Kuznetsov, M. L. (2018). Reaction between indazole and Pd-bound isocyanides—A theoretical mechanistic study. Molecules, 23(11), [2942]. https://doi.org/10.3390/molecules23112942

Vancouver

Casella G, Casarin M, Kukushkin VY, Kuznetsov ML. Reaction between indazole and Pd-bound isocyanides—A theoretical mechanistic study. Molecules. 2018 Нояб. 10;23(11). 2942. https://doi.org/10.3390/molecules23112942

Author

Casella, Girolamo ; Casarin, Maurizio ; Kukushkin, Vadim Yu ; Kuznetsov, Maxim L. / Reaction between indazole and Pd-bound isocyanides—A theoretical mechanistic study. в: Molecules. 2018 ; Том 23, № 11.

BibTeX

@article{2985d753ac6b458bba5262c46e996a62,
title = "Reaction between indazole and Pd-bound isocyanides—A theoretical mechanistic study",
abstract = " The mechanism of the addition of indazole (Ind)—a bifunctional aromatic N,NH-nucleophile—to cyclohexyl isocyanide coordinated to the palladium(II) center in the model complex cis-[PdCl 2 (CNMe)(CNCy)] (1) to give the corresponding aminocarbene ligand was investigated in detail by theoretical (DFT) methods. The most plausible mechanism of this reaction is that of the associative type involving nucleophilic attack of Ind by its unprotonated N atom at the isocyanide carbon atom followed by the stepwise proton transfer from the nucleophile molecule to the isocyanide N atom via deprotonation/protonation steps. Two reaction channels based on two tautomeric forms of indazole were found. The channel leading to the experimentally isolated aminocarbene product is based on the less stable tautomeric form. Another channel based on the more stable tautomer of Ind is slightly kinetically more favorable but it is endergonic. Thus, the regioselectivity of this reaction is thermodynamically rather than kinetically driven. The bonding situation in key species was analyzed. ",
keywords = "Activation of small molecules, DFT calculations, Isocyanides, Nitriles, Nucleophilic addition, Reaction mechanism",
author = "Girolamo Casella and Maurizio Casarin and Kukushkin, {Vadim Yu} and Kuznetsov, {Maxim L.}",
year = "2018",
month = nov,
day = "10",
doi = "10.3390/molecules23112942",
language = "English",
volume = "23",
journal = "Molecules",
issn = "1420-3049",
publisher = "MDPI AG",
number = "11",

}

RIS

TY - JOUR

T1 - Reaction between indazole and Pd-bound isocyanides—A theoretical mechanistic study

AU - Casella, Girolamo

AU - Casarin, Maurizio

AU - Kukushkin, Vadim Yu

AU - Kuznetsov, Maxim L.

PY - 2018/11/10

Y1 - 2018/11/10

N2 - The mechanism of the addition of indazole (Ind)—a bifunctional aromatic N,NH-nucleophile—to cyclohexyl isocyanide coordinated to the palladium(II) center in the model complex cis-[PdCl 2 (CNMe)(CNCy)] (1) to give the corresponding aminocarbene ligand was investigated in detail by theoretical (DFT) methods. The most plausible mechanism of this reaction is that of the associative type involving nucleophilic attack of Ind by its unprotonated N atom at the isocyanide carbon atom followed by the stepwise proton transfer from the nucleophile molecule to the isocyanide N atom via deprotonation/protonation steps. Two reaction channels based on two tautomeric forms of indazole were found. The channel leading to the experimentally isolated aminocarbene product is based on the less stable tautomeric form. Another channel based on the more stable tautomer of Ind is slightly kinetically more favorable but it is endergonic. Thus, the regioselectivity of this reaction is thermodynamically rather than kinetically driven. The bonding situation in key species was analyzed.

AB - The mechanism of the addition of indazole (Ind)—a bifunctional aromatic N,NH-nucleophile—to cyclohexyl isocyanide coordinated to the palladium(II) center in the model complex cis-[PdCl 2 (CNMe)(CNCy)] (1) to give the corresponding aminocarbene ligand was investigated in detail by theoretical (DFT) methods. The most plausible mechanism of this reaction is that of the associative type involving nucleophilic attack of Ind by its unprotonated N atom at the isocyanide carbon atom followed by the stepwise proton transfer from the nucleophile molecule to the isocyanide N atom via deprotonation/protonation steps. Two reaction channels based on two tautomeric forms of indazole were found. The channel leading to the experimentally isolated aminocarbene product is based on the less stable tautomeric form. Another channel based on the more stable tautomer of Ind is slightly kinetically more favorable but it is endergonic. Thus, the regioselectivity of this reaction is thermodynamically rather than kinetically driven. The bonding situation in key species was analyzed.

KW - Activation of small molecules

KW - DFT calculations

KW - Isocyanides

KW - Nitriles

KW - Nucleophilic addition

KW - Reaction mechanism

UR - http://www.scopus.com/inward/record.url?scp=85056498005&partnerID=8YFLogxK

U2 - 10.3390/molecules23112942

DO - 10.3390/molecules23112942

M3 - Article

C2 - 30423833

AN - SCOPUS:85056498005

VL - 23

JO - Molecules

JF - Molecules

SN - 1420-3049

IS - 11

M1 - 2942

ER -

ID: 41787136