二（吡啶-2-基）氨基取代的1,10-菲咯啉及其Ru（II）-Pd（II）双核配合物：无铜Sonogashira反应中的合成、表征及应用

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 reaction.

作者信息

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

机构信息

Lomonosov Moscow State University, Department of Chemistry, 1-3, Leninskie Gory, Moscow, 119991, Russia.

P.N. Lebedev Physical Institute of the Russian Academy of Sciences, 53, Leninsky Prospect, Moscow, 119991, Russia.

出版信息

Dalton Trans. 2024 Oct 22;53(41):17021-17035. doi: 10.1039/d4dt02067g.

DOI:10.1039/d4dt02067g

PMID:39355929

Abstract

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)Ru(Phen-NPy2)PdCl (Ru(Phen-NPy2)Pd) in good yields 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 Ru potential in Ru(Phen-NPy2)Pd complexes showed no significant dependence on the dpa position, while the Pd 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 Ag/AgCl, KCl, 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)(PF)/(RNPy)PdCl.

摘要

带有Ru(II)光活性中心的双核配合物对于开发用于许多光催化反应的高效双催化剂具有重要意义。合成了双齿多吡啶配体，即双(吡啶-2-基)氨基-1,10-菲咯啉，在1,10-菲咯啉核的3、4或5位含有一个额外的配位位点（双(吡啶-2-基)胺，dpa）（Phen-3NPy2、Phen-4NPy2和Phen-5NPy2）。它们被用作桥连配体，通过逐步络合以良好的产率得到双核配合物(bpy)Ru(Phen-NPy2)PdCl（Ru(Phen-NPy2)Pd）。通过核磁共振光谱和X射线单晶分析确定，在这些配合物中，Ru(II)与1,10-菲咯啉配位，而Pd(II)与dpa螯合部分结合。研究了dpa在菲咯啉环中的位置对Ru(Phen-NPy2)Pd配合物的结构、光学和电化学性质的影响。这些配合物在氩气饱和的MeCN溶液中表现出光致发光，最大发射波长在615 - 625 nm范围内，Ru(Phen-NPy2)配合物的发射量子产率在0.11至0.15之间，双核Ru(Phen-NPy2)Pd配合物的发射量子产率在0.018至0.026之间。所有配合物在370 - 470 nm范围内吸收可见光，具有高消光系数，可被视为有用的光催化剂。Ru(Phen-NPy2)Pd配合物中的Ru电位对dpa位置没有明显依赖性，而Ru(Phen-3NPy2)Pd和Ru(Phen-4NPy2)Pd的Pd还原电位明显低于Ru(Phen-5NPy2)Pd（分别为 - 0.57 V和 - 0.72 V Ag/AgCl，KCl）。这些配合物在蓝色发光二极管（12 W）照射下用作无铜Sonogashira偶联反应中的光活化前催化剂。与混合催化体系Ru(bpy)(PF)/(RNPy)PdCl相比，当使用Ru(Phen-4NPy2)Pd和Ru(Phen-3NPy2)Pd作为催化剂前体时，反应速度大约快三倍。