Effects of the halogenido ligands on the Kumada-coupling catalytic activity of [Ni{tBuN(PPh2)2-.kappa.2P}X2], X = Cl, Br, I, complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389013%3A_____%2F22%3A00553702" target="_blank" >RIV/61389013:_____/22:00553702 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2022/RA/D1RA04572E" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2022/RA/D1RA04572E</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/D1RA04572E" target="_blank" >10.1039/D1RA04572E</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Effects of the halogenido ligands on the Kumada-coupling catalytic activity of [Ni{tBuN(PPh2)2-.kappa.2P}X2], X = Cl, Br, I, complexes

Popis výsledku v původním jazyce

Novel nickel(II) complexes bearing (tbutyl)bis(diphenylphosphanyl)amine and different halogenido ligands, [Ni(P,P)X2] = [Ni{tBuN(PPh2)2-κ2P}X2], (X = Cl, Br, I) are prepared, characterized by IR and NMR spectroscopy, mass spectrometry and X-ray crystallography, and tested as catalysts in the Kumada cross-coupling reaction of model substituted iodobenzenes and p-tolylmagnesium bromide. The data obtained together with DFT calculations indicate that these new catalysts operate in the Ni(I)–Ni(III) mode. The highest catalytic activity and selectivity are exhibited by [Ni(P,P)Cl2], which is most easily reduced by the used Grignard reagent to the Ni(I) state. This process is much more energy demanding in the case of the bromido and iodido complexes, causing the appearance of the induction period. [Ni(P,P)Cl2] is also very active in the cross-couplings of substrates with iodine atoms sterically shielded by ortho substituents. The data obtained are in good accordance with the described positive effect of the increased electron-releasing power of N-substituents R′ on the overall catalytic performance of [Ni{R′N(PPh2)2-κ2P}X2] complexes.

Název v anglickém jazyce

Effects of the halogenido ligands on the Kumada-coupling catalytic activity of [Ni{tBuN(PPh2)2-.kappa.2P}X2], X = Cl, Br, I, complexes

Popis výsledku anglicky

Novel nickel(II) complexes bearing (tbutyl)bis(diphenylphosphanyl)amine and different halogenido ligands, [Ni(P,P)X2] = [Ni{tBuN(PPh2)2-κ2P}X2], (X = Cl, Br, I) are prepared, characterized by IR and NMR spectroscopy, mass spectrometry and X-ray crystallography, and tested as catalysts in the Kumada cross-coupling reaction of model substituted iodobenzenes and p-tolylmagnesium bromide. The data obtained together with DFT calculations indicate that these new catalysts operate in the Ni(I)–Ni(III) mode. The highest catalytic activity and selectivity are exhibited by [Ni(P,P)Cl2], which is most easily reduced by the used Grignard reagent to the Ni(I) state. This process is much more energy demanding in the case of the bromido and iodido complexes, causing the appearance of the induction period. [Ni(P,P)Cl2] is also very active in the cross-couplings of substrates with iodine atoms sterically shielded by ortho substituents. The data obtained are in good accordance with the described positive effect of the increased electron-releasing power of N-substituents R′ on the overall catalytic performance of [Ni{R′N(PPh2)2-κ2P}X2] complexes.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10404 - Polymer science

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

RSC Advances

ISSN

2046-2069

e-ISSN

2046-2069

Svazek periodika

12

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

10

Strana od-do

2227-2236

Kód UT WoS článku

000742389300001

EID výsledku v databázi Scopus

2-s2.0-85123785785