X-ray structure and cytotoxic activity of a picolinate ruthenium(II)-arene complex

Ivanović, Ivanka; Grgurić-Šipka, Sanja; Gligorijević, Nevenka; Radulović, Siniša; Roller, Alexander; Tešić, Živoslav; Keppler, Bernhard K.

doi:10.2298/jsc100517017i

Cited by 25 publications

(16 citation statements)

References 43 publications

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“…The 1 H NMR spectra of complexes [Ru]‐1 – [Ru]‐10 depicts an analogous trend, where a downfield shift in the chemical shifts of the protons associated with the ligands is observed, compared with the free ligands, suggesting the coordination of the ligand to the ruthenium metal center. The 1 H NMR resonances for protons corresponding to the ruthenium‐coordinated η 6 ‐arene ring are also observed in the expected region for all complexes , , . The FTIR and UV/Visible spectra recorded for the synthesized complexes are also in accordance with the previous reports , .…”

Section: Resultssupporting

confidence: 87%

“…The 1 H NMR resonances for protons corresponding to the ruthenium‐coordinated η 6 ‐arene ring are also observed in the expected region for all complexes , , . The FTIR and UV/Visible spectra recorded for the synthesized complexes are also in accordance with the previous reports , . The ESI mass spectra of the complexes [Ru]‐1 and [Ru]‐6 shows peaks corresponding to the [M – Cl] + ions, while the rest of the cationic complexes display peaks for the [M] + ions, with the characteristic Ru isotopic patterns.…”

Section: Resultssupporting

confidence: 87%

“…Complexes [Ru]‐1 – [Ru]‐2 , [Ru]‐4 – [Ru]‐7 , [Ru]‐9 , and [Ru]‐10 , with the general formula [(η 6 ‐arene)RuCl(κ 2 ‐L)] n + , where η 6 ‐arene = C 6 H 6 or C 10 H 14 , L = L1 – L2 , L4 , and L5 and n = 0, +1, were obtained by treating the respective [{(η 6 ‐arene)RuCl 2 } 2 ] compound with ligands L1 – L2 , L4 , and L5 in methanol. [15d], Complexes [Ru]‐3 and [Ru]‐8 were obtained by stirring ligand L3 with [{(η 6 ‐arene)RuCl 2 } 2 ] (η 6 ‐arene = η 6 ‐C 10 H 14 and η 6 ‐C 6 H 6 ) in dichloromethane at room temperature. The synthesized complexes have been well‐characterized by various spectro‐analytical techniques, which further authenticates the proposed structure shown in Scheme .…”

Section: Resultsmentioning

confidence: 99%

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Ligand‐Tuned C–H Bond Activation/Arylation of 2‐Arylpyridines over Pyridine‐Based N,O/N,N Ligated Ruthenium–Arene Complexes

et al. 2018

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Water-soluble ruthenium(II)-arene complexes [(η 6arene)Ru(κ 2 -L)] n+ (n = 0, 1) ([Ru]-1-[Ru]-10) containing pyridine-based bischelating N,O/N,N donor ligands (L1-L5) are synthesized and employed for the catalytic C-H bond activation/ arylation of a wide range of 2-phenylpyridines and aryl halides in water, affording the corresponding mono-and biarylated products. Exploring the reactivity of the synthesized complexes, our investigations, including time-dependent 1 H NMR spectroscopic studies with ruthenium-arene catalysts, demonstrate a remarkable structure-activity relationship for the ligand-tuned C-H activation/arylation of 2-phenylpyridine, where the complexes with bischelating N,O donor-based ligands (acteylpyridine and picolinate) outperform those with N,N donor ligands [a] ditives, driven by steric bulkiness, in tuning the selectivity of C-H arylation products. [13] Later, we also explored aniline-based ruthenium-arene complexes for C-H bond arylation in water, where the strength of the aniline-ruthenium bond and substitution on the aniline ligand were found to be crucial factors for tuning the selectivity of mono-versus biarylated products during the reaction. [14] Further, in our deliberate efforts to develop an efficient catalytic system for C-H activation/functionalization reactions, [13,14] herein we have synthesized a series of ruthenium(II)-arene complexes containing pyridine-based N,O and N,N donor ligands, and we have systematically investigated their catalytic performance for ortho C-H bond activation/arylation of 2-phenylpyridine with several aryl halides in water. The synthesized ruthenium-arene complexes have been well-characterized using NMR spectroscopy and mass spectrometric analysis, and the molecular structure of a few of the representative complexes have been authenticated by single-crystal X-ray diffraction studies. Attempts have also been made to establish the relationship between the pattern of bonding of the ligands to the ruthenium metal center and the observed catalytic activity of these complexes for ortho C-H bond-activation/arylation reactions using time-scaled 1 H NMR spectroscopy. Results and Discussion Synthesis of Water-Soluble Ruthenium(II)-Arene Complexes [Ru]-1 to [Ru]-10Water-soluble ruthenium-arene complexes ([Ru]-1-[Ru]-10) containing pyridine-based N,O and N,N donor ligands were synthesized in good yield by reacting the respective ruthenium(II)arene dimer with the readily available ortho-substituted pyridine-based N,O/N,N donor bidentate ligands, with substituents ranging from carboxylic [pyridine-2-carboxylic acid (L1)], acetyl [2-acetylpyridine (L2)], ester [2-methylpicolinate (L3)], and imino groups [N-benzyl-pyridylimine (L4) and N-butyl-pyridylimine (L5)], as shown in Scheme 1. Scheme 1. Synthesis of ruthenium-arene complexes [Ru]-1-[Ru]-10 containing pyridine-based N,O and N,N donor ligands.

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Section: Resultssupporting

confidence: 87%

Section: Resultssupporting

confidence: 87%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Ligand‐Tuned C–H Bond Activation/Arylation of 2‐Arylpyridines over Pyridine‐Based N,O/N,N Ligated Ruthenium–Arene Complexes

et al. 2018

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“…The Ru(II) precursor [Ru(η 6 -toluene)Cl(μ-Cl)] 2 and the complexes of picH, 3-Me-picH, 5-BrpicH, 2,4-dipicH 2 and 2,5-dipicH 2 (Chart 1) were obtained according to the literature procedure used for the analogous Ru(η 6 -p-cymene) complexes [25][26][27][28]. Pure compounds (1)(2)(3)(4)(5) were isolated from methanol or 2-propanol with moderate yields 50-58%.…”

Section: Synthesis Characterization and X-ray Diffraction Analysis Omentioning

confidence: 99%

Comparative solution equilibrium and structural studies of half-sandwich ruthenium(II)(η6-toluene) complexes of picolinate derivatives

Poljarević

Gál

May

et al. 2018

Journal of Inorganic Biochemistry

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“…In order to compare the differences in speciation and thus in the stability of the complexes order of biological activity [28,30,36,[47][48][49]. …”

Section: + Hl [Ml] + H + (3)mentioning

confidence: 99%

Solution equilibrium studies of anticancer ruthenium(II)-η6-p-cymene complexes of pyridinecarboxylic acids

et al. 2014

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Stoichiometry and stability of antitumor ruthenium(II)-η 6 -p-cymene complexes of picolinic acid and its 6-methyl and 6-carboxylic acid derivatives were determined by pHpotentiometry, 1 H NMR spectroscopy and UV/Vis spectrophotometry in aqueous solution in the presence or absence of coordinating chloride ions. The picolinates form exclusively monoligand complexes in which they can coordinate via the bidentate (O,N) mode and a chloride or a water molecule is found at the third binding site of the ruthenium(II)-η 6 -p-cymene moiety depending on the conditions. [Ru(η 6 -p-cymene)(L)(H 2 O/Cl)] species are predominant at physiological pH in all studied cases. Hydrolysis of the aqua complex or the chlorido/hydroxido co-ligand exchange results in the formation of the mixed-hydroxido species [Ru(η 6 -p-cymene)(L)(OH)] in the basic pH range. There is no indication for the decomposition of the mono-ligand complexes during 24 h in the ruthenium(II)-η 6 -pcymene−picolinic acid system between pH 3 and 11; however, a slight dissociation with a low reaction rate was found in the other two systems leading to the appearance of the dinuclear trihydroxido-bridged species [Ru 2 (η 6 -p-cymene) 2 (OH) 3 ] + and free ligands at pH > 10. The replacement of the chlorido by an aqua ligand in [Ru(η 6 -p-cymene)(L)Cl] was also monitored and equilibrium constants for the exchange process were determined.

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X-ray structure and cytotoxic activity of a picolinate ruthenium(II)-arene complex

Cited by 25 publications

References 43 publications

Ligand‐Tuned C–H Bond Activation/Arylation of 2‐Arylpyridines over Pyridine‐Based N,O/N,N Ligated Ruthenium–Arene Complexes

Ligand‐Tuned C–H Bond Activation/Arylation of 2‐Arylpyridines over Pyridine‐Based N,O/N,N Ligated Ruthenium–Arene Complexes

Comparative solution equilibrium and structural studies of half-sandwich ruthenium(II)(η6-toluene) complexes of picolinate derivatives

Solution equilibrium studies of anticancer ruthenium(II)-η6-p-cymene complexes of pyridinecarboxylic acids

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