Investigating the Formation Mechanism of Arene Ruthenium Metallacycles by NMR Spectroscopy

Garci, Amine; Gupta, Gajendra; Dalvit, Claudio; Therrien, Bruno

doi:10.1002/ejic.201402639

Cited by 10 publications

(6 citation statements)

References 74 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As commonly observed in dinuclear arene ruthenium clips bridged by hydroxybenzoquinonato ligands, the trans isomer is observed in the crystals of 1a (Figure ). In this dinuclear complex, the Ru···Ru distance is 7.8861(3) Å, which is comparable to the Ru···Ru distances observed in arene ruthenium metallacycles and metallaprisms bridged by analogous hydroxybenzoquinonato spacers.…”

Section: Resultssupporting

confidence: 67%

Tunable Arene Ruthenium Metallaprisms to Transport, Shield, and Release Porphin in Cancer Cells

et al. 2015

Self Cite

View full text Add to dashboard Cite

International audienceThree neutral dinuclear p-cymene ruthenium complexes (1a–1c) of the general formula (p-cymene)2Ru2(μ4-L)Cl2, bridged by substituted hydroxybenzoquinonato spacers (La = 2,5-dihydroxy-3-phenyl-1,4-benzoquinonato; Lb = 2,5-dihydroxy-3,6-diphenyl-1,4-benzoquinonato; Lc = 2,5-dihydroxy-3,6-(3,5-dimethylphenyl)-1,4-benzoquinonato) have been synthesized and characterized. The corresponding p-cymene ruthenium metallaprisms, [{(p-cymene)2Ru2(μ4-L)}3(tpt)2][CF3SO3]6 (2a–2c), were obtained by mixing in methanol the neutral dinuclear complexes 1a–1c, AgCF3SO3, and 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (tpt). In a similar fashion, addition of porphin during the formation of the metallaprisms afforded the host–guest systems [porphin⊂{(p-cymene)2Ru2(μ4-L)}3(tpt)2][CF3SO3]6 ([porphin⊂2][CF3SO3]6). The biological activity of all complexes was estimated on the colon cancer cell line HT-29, showing low cytotoxicity in the dark (IC50 > 5 μM). On the other hand, the phototoxicity of the porphin-in-the-cage systems under standard irradiation conditions (20 J/cm2) is quite spectacular, being in the lower nanomolar range for [porphin⊂2c][CF3SO3]6

show abstract

Section: Resultssupporting

confidence: 67%

Tunable Arene Ruthenium Metallaprisms to Transport, Shield, and Release Porphin in Cancer Cells

et al. 2015

Self Cite

View full text Add to dashboard Cite

show abstract

“…During assembly, two pathways, I and II , can be followed for complexation (Scheme ). During the initial step of pathway II , two bipyridine molecules coordinate to a single diruthenium clip and connect to another diruthenium clip. In this pathway, the positions of the bromophenyl groups are not controllable and types A – D can be formed.…”

Section: Resultsmentioning

confidence: 99%

Selective Self-Assembly of a Rectangular Ruthenium Supramolecule from an Unsymmetrical Bridging Unit

Ryu

Lee

et al. 2019

Inorg. Chem.

View full text Add to dashboard Cite

Herein, we report the synthesis of an unsymmetrical diruthenium bridging unit containing a multidentate oxamate ligand and the subsequent formation of a rectangular supramolecule. The reaction of oxamate 1, 2-((4-bromo-2,6dimethylphenyl)amino)-2-oxo-acetic acid, and [(p-cymene)RuCl 2 ] 2 affords a novel unsymmetrical diruthenium acceptor clip 2, where two ruthenium metal centers are ligated with either [O,O] or [N,O].The molecular clip 2 and bipyridine donor selfassemble to form two-dimensional rectangular supramolecule 3. Self-assembly can produce seven possible isomers depending on the position of the substituted bromoaryl groups. However, 1 H NMR spectroscopic investigation indicated only two different isomers in the reaction mixture. A single isomer is isolated via crystallization, and X-ray crystallography confirms that the product is a C 1 symmetric two-dimensional rectangular supramolecule, in which two bromoaryl groups are located in the farthest position from each other. Theoretical calculations suggest that the self-assembly of supramolecule 3 occurred via 1:1 adducts of the diruthenium molecular clip and bipyridine as an intermediate to predominantly form a single isomer.

show abstract

“…However, both isomers have been observed, and they usually interchanged rapidly in solution. The kinetics of the cis‐trans interconversion depend mostly on the nature of the ligands, and it remains an important factor for the formation of discrete metalla‐assemblies as only a cis ‐coordination can provide a discrete assembly [18] …”

Section: Arene Ruthenium Complexesmentioning

confidence: 99%

Unmasking Arene Ruthenium Building Blocks

Therrien

2020

The Chemical Record

Self Cite

View full text Add to dashboard Cite

We have, like many others, contributed to the development and to the popularity of arene ruthenium assemblies. From early on, our research was driven by applications, mainly biological (therapeutic, drug delivery, DNA interactions, photodynamic therapy, imaging). For nearly 15 years, we have focused on the use of arene ruthenium building block as a tool to construct added‐value objects. In this account, we want to give the basic reasons behind our choice, and uncover our most successful examples, with an emphasis on the foreseen applications.

show abstract

Investigating the Formation Mechanism of Arene Ruthenium Metallacycles by NMR Spectroscopy

Cited by 10 publications

References 74 publications

Tunable Arene Ruthenium Metallaprisms to Transport, Shield, and Release Porphin in Cancer Cells

Tunable Arene Ruthenium Metallaprisms to Transport, Shield, and Release Porphin in Cancer Cells

Selective Self-Assembly of a Rectangular Ruthenium Supramolecule from an Unsymmetrical Bridging Unit

Unmasking Arene Ruthenium Building Blocks

Contact Info

Product

Resources

About