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Di(pyridin-2-yl)amino-substituted 1,10-phenanthrolines and their Ru(II)–Pd(II) dinuclear complexes: synthesis, characterization and application in Cu-free Sonogashira reactionстатья
Статья опубликована в высокорейтинговом журнале
Статья опубликована в журнале из списка Web of Science и/или Scopus- Авторы: Ionova Violetta A., Dmitrieva Alena V., Abel Anton S., Sergeev Aleksandr D., Evko Grigory S., Yakushev Alexei A., Gontcharenko Victoria E., Nefedov Sergei E., Roznyatovsky Vitaly A., Cheprakov Andrey V., Averin Alexei D., Magdesieva Tatiana V., Beletskaya Irina P.
- Журнал: Dalton Transactions
- Том: 53
- Номер: 41
- Год издания: 2024
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- Первая страница: 17021
- Последняя страница: 17035
- DOI: 10.1039/d4dt02067g
- Аннотация: Dinuclear complexes bearing Ru(II) photoactive centers are of interest for the development of efficient dual catalysts for many photocatalyzed reactions. Ditopic polypyridine ligands, bis(pyridin-2-yl)amino-1,10-phenanthrolines, containing an additional coordination site (bis(pyridin-2-yl)amine, dpa) at positions 3, 4 or 5 of the 1,10-phenanthroline core (Phen-3NPy2, Phen-4NPy2 and Phen-5NPy2) were synthesized. They were used as bridging ligands to obtain dinuclear complexes [(bpy)2Ru(Phen-NPy2)PdCl2](PF6)2 (Ru(Phen-NPy2)Pd) in good yields via stepwise complexation. In these complexes Ru(II) is coordinated to 1,10-phenanthroline, while Pd(II) is bound to the dpa chelating moiety, as established by NMR spectroscopy and X-ray single crystal analysis. The influence of the position of dpa in the phenanthroline ring on the structural, optical and electrochemical properties of Ru(Phen-NPy2)Pd complexes was studied. The complexes exhibit photoluminescence in argon-saturated MeCN solution with maxima in the range of 615–625 nm, with emission quantum yields ranging from 0.11 to 0.15 for Ru(Phen-NPy2) complexes and from 0.018 to 0.026 for dinuclear Ru(Phen-NPy2)Pd complexes. All the complexes absorb visible light in the range of 370–470 nm with high extinction coefficients and can be considered useful as photocatalysts. The Ru2+/3+ potential in Ru(Phen-NPy2)Pd complexes showed no significant dependence on the dpa position, while the Pd2+/0 reduction potential was significantly lower for Ru(Phen-3NPy2)Pd and Ru(Phen-4NPy2)Pd, than for Ru(Phen-5NPy2)Pd (−0.57 V and −0.72 V vs. Ag/AgCl, KCl(sat.), respectively). The complexes were used as photoactivated precatalysts in Cu-free Sonogashira coupling under blue LEDs (12 W) irradiation. The reaction proceeded roughly three times faster when Ru(Phen-4NPy2)Pd and Ru(Phen-3NPy2)Pd were used as catalyst precursors compared to the mixed catalytic system Ru(bpy)3(PF6)2/(RNPy2)PdCl2.
- Добавил в систему: Евко Григорий Сергеевич
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