Di(pyridin-2-yl)amino-substituted 1,10-phenanthrolines and their Ru(<sc>ii</sc>)-Pd(<sc>ii</sc>) dinuclear complexes: synthesis, characterization and application in Cu-free Sonogashira reaction

被引：1

作者：

Ionova, Violetta A. ^{[1
]}

Dmitrieva, Alena V. ^{[1
]}

Abel, Anton S. ^{[1
]}

Sergeev, Aleksandr D. ^{[1
]}

Evko, Grigory S. ^{[1
]}

Yakushev, Alexei A. ^{[1
]}

Gontcharenko, Victoria E. ^{[2
,3
]}

Nefedov, Sergei E. ^{[4
]}

Roznyatovsky, Vitaly A. ^{[1
]}

Cheprakov, Andrey V. ^{[1
]}

Averin, Alexei D. ^{[1
]}

Magdesieva, Tatiana V. ^{[1
]}

Beletskaya, Irina P. ^{[1
,5
]}

机构：

[1] Lomonosov Moscow State Univ, Dept Chem, 1-3, Leninskie Gory, Moscow 119991, Russia

[2] Russian Acad Sci, PN Lebedev Phys Inst, 53,Leninsky Prospect, Moscow 119991, Russia

[3] Natl Res Univ, Fac Chem, Higher Sch Econ, 20 Miasnitskaya St, Moscow 101000, Russia

[4] RAS, NS Kurnakov Inst Gen & Inorgan Chem, Leninsky pr,31, Moscow 119991, Russia

[5] Russian Acad Sci, Frumkin Inst Phys Chem & Electrochem, Leninsky Pr 31, Moscow 119071, Russia

来源：

DALTON TRANSACTIONS | 2024年 / 53卷 / 41期

关键词：

CROSS-COUPLING REACTIONS; COOPERATIVE PHOTOREDOX; HYDROGEN GENERATION; BRIDGING LIGAND; PALLADIUM; METAL; REDUCTION; PHOTOCATALYSTS; LUMINESCENT; CATALYSIS;

D O I：

10.1039/d4dt02067g

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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-3NPy(2), Phen-4NPy(2) and Phen-5NPy(2)) were synthesized. They were used as bridging ligands to obtain dinuclear complexes [(bpy)(2)Ru(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-3NPy(2))Pd and Ru(Phen-4NPy(2))Pd, than for Ru(Phen-5NPy(2))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-4NPy(2))Pd and Ru(Phen-3NPy(2))Pd were used as catalyst precursors compared to the mixed catalytic system Ru(bpy)3(PF6)(2)/(RNPy2)PdCl2.

引用

页码：17021 / 17035

页数：15

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