Rational Synthesis of Heteroleptic Tris(chelate) Ruthenium Complexes [RuII(2-Ph-2′-Py)(L∧L)(L′∧L′)]PF6 by Selective Substitution of the Ligand Trans to the Ruthenated Phenyl Ring

Boff, Bastien; Ali, Moussa; Alexandrova, Larissa; Espinosa‐Jalapa, Noel Angel; Saavedra-Díaz, Rafael Omar; Lagadec, Ronan Le; Pfeffer, Michel

doi:10.1021/om400611t

Cited by 17 publications

(15 citation statements)

References 22 publications

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“…The synthesized cycloruthenated complexes produced significant cytotoxic effects in mammalian tumor cells that were similar to cisplatin and were less likely to produce neurotoxicity compared to cisplatin. 226,227 Fetzer et al . synthesized a series of cycloruthenated compounds with N-C-N and N-N-C pincer derivatives (Fig.…”

Section: Ruthenium(ii) Polypyridyl Complexesmentioning

confidence: 99%

The development of anticancer ruthenium(ii) complexes: from single molecule compounds to nanomaterials

et al. 2017

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Cancer is rapidly becoming the top killer in the world. Most of the FDA approved anticancer drugs are organic molecules, while metallodrugs are very scarce. The advent of first metal based therapeutic agent, cisplatin, launched a new era in the application of transition metal complexes for therapeutic design. Due to their unique and versatile biochemical properties, ruthenium-based compounds have emerged as promising anti-cancer agents that serve as alternatives to cisplatin and its derivertives. The ruthenium(III) complexes have successfully been used in clinical research and their mechanisms of anticancer action have been reported in large volumes over the past few decades. Ruthenium(II) complexes have also attracted significant attention as anticancer candidates; however, only few of them have been reported comprehensively. In this review, we discuss the development of ruthenium(II) complexes as anticancer candidates and biocatalysts, including arene ruthenium complexes, polypyridyl ruthenium complexes, and ruthenium nanomaterial complexes. This review focuses on the likely mechanisms of action of ruthenium(II)-based anticancer drugs and the relationship between their chemical structures and biological properties. This review also highlights the catalytic activity and the photoinduced activation of ruthenium(II) complexes, their targeted delivery, and their activity in nanomaterial systems.

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Section: Ruthenium(ii) Polypyridyl Complexesmentioning

confidence: 99%

The development of anticancer ruthenium(ii) complexes: from single molecule compounds to nanomaterials

et al. 2017

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“…The four cycloruthenated complexes [ 2 ]PF 6 –[ 5 ]PF 6 were prepared as shown in Scheme , following the synthetic route established by the Pfeffer group . The dimer [(η 6 ‐C 6 H 6 )RuCl(μ‐Cl)] 2 was heated in CH 3 CN at 45 °C together with NaOH, KPF 6 , and Hphpy to yield the cycloruthenated complex [Ru(phpy)(CH 3 CN) 4 ]PF 6 .…”

Section: Resultsmentioning

confidence: 99%

“…However, Pfeffer et al. recently showed that this structural assignment might not be correct . CH 3 CN is a very good ligand for ruthenium(II), and in order to turn it into a good leaving group the complex must first isomerize (either thermally or photochemically) so that one CH 3 CN ligand becomes trans to the carbon ligand, which is a very reactive position due to the trans effect of the C donor atom .…”

Section: Resultsmentioning

confidence: 99%

“…recently showed that this structural assignment might not be correct . CH 3 CN is a very good ligand for ruthenium(II), and in order to turn it into a good leaving group the complex must first isomerize (either thermally or photochemically) so that one CH 3 CN ligand becomes trans to the carbon ligand, which is a very reactive position due to the trans effect of the C donor atom . This mechanism also seems to occur for the coordination of N,S ligands, as the obtained isomer of [ 4 ] + has the N atom of the last incoming ligand trans to the carbon atom of phpy − , as proven by NOESY studies and X‐ray diffraction analysis.…”

Section: Resultsmentioning

confidence: 99%

“…The four cycloruthenated complexes [2]PF 6 -[5]PF 6 werep repared as shown in Scheme1,f ollowing the synthetic route establishedb yt he Pfeffer group. [28,29] The dimer [(h 6 -C 6 H 6 )RuCl(m-Cl)] 2 was heated in CH 3 CN at 45 8Ct ogether with NaOH, KPF 6 , and Hphpy to yield the cycloruthenated complex [Ru(phpy)(CH 3 CN) 4 ]PF 6 .A fter purification by column chromatography on alumina using CH 2 Cl 2 as eluent, the complex was furtherr e-acted with 0.8 equiv of bpy in CH 2 Cl 2 at room temperature for 20 ht oa fford cis-[Ru(bpy)(phpy)(CH 3 CN) 2 ]PF 6 ([1a]PF 6 ), with the carbon donor atom trans to bpy.A chieving the controlled coordination of only one equivalent of bpy is not straightforward, as [Ru(bpy) 2 (phpy)]PF 6 is readily formedi nt his reaction. To avoid formation of this product, only 0.8 equiv of bpy was added to the reaction mixture.…”

Section: Synthesismentioning

confidence: 99%

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Selective Preparation of a Heteroleptic Cyclometallated Ruthenium Complex Capable of Undergoing Photosubstitution of a Bidentate Ligand

Cuello-Garibo

James

Siegler³

et al. 2018

Chemistry A European J

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Cyclometallated ruthenium complexes typically exhibit red‐shifted absorption bands and lower photolability compared to their polypyridyl analogues. They also have lower symmetry, which sometimes makes their synthesis challenging. In this work, the coordination of four N,S bidentate ligands, 3‐(methylthio)propylamine (mtpa), 2‐(methylthio)ethylamine (mtea), 2‐(methylthio)ethyl‐2‐pyridine (mtep), and 2‐(methylthio)methylpyridine (mtmp), to the cyclometallated precursor [Ru(bpy)(phpy)(CH 3 CN) 2 ] + (bpy=2,2′‐bipyridine, Hphpy=2‐phenylpyridine) has been investigated, furnishing the corresponding heteroleptic complexes [Ru(bpy)(phpy)(N,S)]PF 6 ([ 2 ]PF 6 –[ 5 ]PF 6 , respectively). The stereoselectivity of the synthesis strongly depended on the size of the ring formed by the Ru‐coordinated N,S ligand, with [ 2 ]PF 6 and [ 4 ]PF 6 being formed stereoselectively, but [ 3 ]PF 6 and [ 5 ]PF 6 being obtained as mixtures of inseparable isomers. The exact stereochemistry of the air‐stable complex [ 4 ]PF 6 was established by a combination of DFT, 2D NMR, and single‐crystal X‐ray crystallographic studies. Finally, [ 4 ]PF 6 was found to be photosubstitutionally active under irradiation with green light in acetonitrile, which makes it the first cyclometallated ruthenium complex capable of undergoing selective photosubstitution of a bidentate ligand.

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Ruthenium Anticancer Agents—From Cisplatin Analogues to Rational Drug Design

Adams

Hanif

Hartinger

2017

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The discovery of cisplatin has triggered research in metal‐based anticancer agents. Ruthenium complexes have been investigated as chemotherapeutics for more than 30 years. In this article, we review the early steps of Ru‐based drug development, which was often based on the structural similarity to cisplatin, and led eventually to the clinical trials of KP1019/KP1339 and NAMI‐A and the emergence of the organometallic RAPTA and RAED compound series. The unique modes of action of Ru compounds equip them with their special pharmacological properties. Especially in the past decades, many rationally designed Ru complexes have been reported to expand the range of compound types, and therewith the modes of action these compounds follow. This article covers many of the reported novel approaches and newer developments in the field, demonstrating in some cases properties advantageous to that of platinum anticancer agents and opening the route to new generations of metal‐based anticancer agents.

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Rational Synthesis of Heteroleptic Tris(chelate) Ruthenium Complexes [Ru^II(2-Ph-2′-Py)(L^∧L)(L′^∧L′)]PF₆ by Selective Substitution of the Ligand Trans to the Ruthenated Phenyl Ring

Cited by 17 publications

References 22 publications

The development of anticancer ruthenium(ii) complexes: from single molecule compounds to nanomaterials

The development of anticancer ruthenium(ii) complexes: from single molecule compounds to nanomaterials

Selective Preparation of a Heteroleptic Cyclometallated Ruthenium Complex Capable of Undergoing Photosubstitution of a Bidentate Ligand

Ruthenium Anticancer Agents—From Cisplatin Analogues to Rational Drug Design

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