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Monocationic arene ruthenium complexes (RuL1–RuL4) incorporating phenothiazinyl-hydrazinyl-thiazole ligands (L1–L4) have been synthesized, characterized and evaluated as anticancer agents. Their cytotoxicity, antiproliferative activity and alteration of apoptotic gene expression were studied on three cancer cell lines, a double positive breast canc...
Colorectal cancer (CRC) is the third most common cancer in the world, with an ongoing rising incidence. Despite secure advancements in CRC treatments, challenges such as side effects and therapy resistance remain to be addressed. Photodynamic therapy (PDT) emerges as a promising modality, clinically used in treating different diseases, including ca...
Three bis(imidazo[1,5‐a]pyridine)methane derivatives (bis(1‐methylimidazo[1,5‐a]pyridin‐3‐yl)methane, LH; 3,3’‐(ethane‐1,1‐diyl)bis(1‐methylimidazo[1,5‐a]pyridine) LMe; 3,3’‐(2‐phenylethane‐1,1‐diyl)bis(1‐methylimidazo[1,5‐a]pyridine), LBz) have been synthesized, and fully characterized in solution (¹H and ¹³C NMR spectra) and in the solid state (X...
Treatment regimens are regularly evolving alongside novel therapies and drugs. Such evolution is necessary to circumvent resistance mechanisms and to give patients the best possible health care. When dealing with cancer, most regimens involve multiple treatments (surgery, radiation therapy, chemotherapy, immunotherapy, etc.). The purpose of this st...
Treatment regimens are regularly evolving, together with novel therapies and drugs. Such evolution is necessary to circumvent resistance mechanisms and to give patients the best possible health care. When dealing with cancer, most regimens involve multiple treatments (surgery, radiation therapy, chemotherapy, immunotherapy, etc.). The purpose of th...
Five bis(alkynyl)boranes with a (imidazo[1,5-a]pyridin-3-yl)phenolate ligand have been synthesized and characterized both in solution (1H, 13C, 11B, 19F NMR) and in the solid state (X-ray). All derivatives, differing for the substituent R (H, Me, OMe, CF3, NMe2) in the para position of the phenylacetylene moieties, displayed blue fluorescence emiss...
Photodynamic therapy (PDT) is an interesting and promising approach to tackle a broad spectrum of cancer. With the combination of a photosensitizer, light and oxygen, PDT achieves a unique selectivity by the production of localized reactive oxygen species (ROS) inside cells, which leads to their destruction. In addition, the luminescence properties...
Low oxygen concentration in solid cancer tumors leads to resistance, especially when dealing with photodynamic therapy (PDT) treatments. In fact, the presence of oxygen is mandatory to obtain an efficient PDT treatment. The synthesis of new oxygen carriers, specifically targeting cancer cells, appears to be an elegant strategy to tackle this issue....
Colorectal cancer (CRC) is one of the most frequently diagnosed cancers worldwide and one of the main causes of cancer deaths in the global population. First-line treatment usually includes surgical procedures followed by combination chemotherapy. Despite the improvements in CRC treatments, the mortality rate remains very high, leading consequently...
Photodynamic therapy (PDT) is an interesting and promising approach to tackle a broad spectrum of cancer types. With the combination of a photosensitizer, light and oxygen, PDT achieves a unique selectivity by the production of localized reactive oxygen species (ROS) inside cells, which leads to their destruction. In addition, the luminescence prop...
The effect of dimethyl sulfoxide (DMSO) in rheumatoid arthritis (RA) human fibroblast-like synoviocytes (FLSs) has been studied on five different samples harvested from the joints (fingers, hands and pelvis) of five women with RA. At high concentrations (>5%), the presence of DMSO induces the cleavage of caspase-3 and PARP-1, two phenomena associat...
Two mixed ligand copper(I) complexes, [Cu(PPh3)3(κ‐O‐mand)] (CuP3M) and [Cu(PPh3)2(κ²‐O,O’‐mand)] (CuP2M) (mand=dl‐mandelate) were synthesized and fully characterized. The different coordination modes of the α‐hydroxycarboxylate ligand in CuP2M and CuP3M are clearly demonstrated by infrared spectroscopy, with the asymmetric νC=O stretching being ob...
Ruthenium-based assemblies containing tetrapyridylporphyrins (TPyP) in their structure have been evaluated as photosensitizers (PS) to treat rheumatoid arthritis (RA) by photodynamic therapy (PDT). TPyP is useless by itself as a PS due to its low solubility in biological media, however, incorporated in metallacages it can be internalized in cells....
For the first time, ruthenium-based assemblies have been used as carriers for photosensitizers in the treatment of rheumatoid arthritis by photodynamic therapy (PDT). These metallacages are totally soluble in physiological media and can transport photosensitizers (PS) in their cavity. After an incubation period, the PS is released in the cytoplasm...
Four tetrapyridylporphyrin and four dipyridylporphyrin arene ruthenium complexes have been synthesized and characterized. In these complexes, the porphyrin core is either metal-free or occupied by zinc, and the arene ligand of the arene ruthenium units are either the standard methyl-isopropyl-benzene ([Formula: see text]cymene) or the less common p...
Several boron compounds with 2‐(imidazo[1,5‐a]pyridin‐3‐yl)phenols, differentiated by the nature of the substituent (R) in the para position of the hydroxy group, have been synthesized and thoroughly characterized both in solution (¹H, ¹³C, ¹¹B, ¹⁹F NMR) and in the solid state (X‐ray). All derivatives displayed attractive photophysical properties l...
The Schiff-base 5-methyl-4-{(pyridin-2-ylmethylene)amino}-4H-1,2,4-triazole-3-thiol (L-H) reacts in alcoholic solution (methanol, ethanol, isopropanol) at room temperature with the dinuclear precursor [(η⁶-MeC6H4Prⁱ)RuCl2]2 to give a series of neutral complexes of the general formula (η⁶-MeC6H4Prⁱ)Ru(L-OR) (R = Me, 1; R = Et, 2; R = Prⁱ, 3). In the...
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...
Early cancer detection and perfect understanding of the disease are imperative towards efficient treatments. And it is straightforward that, for choosing a specific cancer treatment methodology, diagnostic agents undertake a critical role. Imaging is an extremely intriguing tool since it is not only assuming a follow up to treatments to survey the...
In Nature, metal ions play critical roles at different levels, and they are often found in proteins. Therefore, metal ions are naturally incorporated in hydrogen-bonded systems. In addition, the combination of metal coordination and hydrogen bonds have been used extensively to develop supramolecular materials. However, despite this win-win combinat...
Some (tetrahydroimidazo[1,5-a]pyridin-3-yl)phenols were reacted with boron trifluoride diethyl etherate and the resulting BF2-functionalized compounds were fully characterized both in solution using ¹H, ¹³C, ¹¹B, ¹⁹F NMR spectroscopy and in the solid state (infrared, fluorescence, X-ray). When excited with UV light these boron difluoride derivative...
Liquid crystals are among us, in living organisms and in electronic devices, and they have contributed to the development of our modern society. Traditionally developed by organic chemists, the field of liquid-crystalline materials is now involving chemists and physicists of all domains (computational, physical, inorganic, supramolecular, electro-c...
Neutral piano-stool complexes of the general formula [(η⁵-C5Me5)Rh(L-OR)] (R = Me, 1; R = Et, 2; R = Prⁱ, 3) have been prepared in alcohols (methanol, 1; ethanol, 2; isopropanol, 3) from the Schiff-base 5-methyl-4-{(pyridin-2-ylmethylene)amino}-4H-1,2,4-triazole-3-thiol (L-H) and the dinuclear precursor [(η⁵-C5Me5)RhCl2]2. Concomitant with the coor...
Photodynamic Therapy (PDT) has become one of the most promising treatment against autoimmune diseases, such as rheumatoid arthritis (RA), as well as in the treatment of different types of cancer, since it is a non-invasive method and easy to carry out. The three main ingredients of PDT are light irradiation, oxygen, and a photosensitizer (PS). Ligh...
The dinuclear copper(I) complex [Cu2(µ-dppm)2(lact)(µ-lact)] (1) (dppm = bis(diphenylphosphino)methane; lact = L-(+)-lactate) was synthesized and fully characterized both in solution and solid state. Variable temperature NMR experiments (1H and 31P), conductivity measurements and infrared spectroscopy, suggest the occurrence of a fluxional behavior...
The human genome is replete with repetitive DNA sequences that can fold into thermodynamically stable secondary structures such as hairpins and quadruplexes. Cellular enzymes exist to cope with these structures whose stable accumulation would result in DNA damage through interference with DNA transactions such as transcription and replication. Ther...
A series of homoleptic zinc(II) complexes of the general formula [Zn(LR)2] (HLR: (imidazo[1,5‐a]pyrid‐3‐yl)phenol; R: para‐substituent to the phenol) have been synthesized. The single‐crystal X‐ray structure analysis of complex [Zn(LH)2] (1) confirmed the expected N,O‐bidentate coordination of LR, via the pyridine‐like nitrogen of the imidazo[1,5‐a...
A series of mono-cationic half-sandwich rhodium(III) complexes have been synthesized in methanol using phenylhydrazone-derived ligands (L 1 –L 6 ) and the starting precursor [(η ⁵ -C 5 Me 5 ) 2 Rh 2 (μ-Cl) 2 Cl 2 ] in a 2:1 molar ratio. The N,N′-phenylhydrazone complexes have been isolated as tetraphenylborate salts. All complexes were characterize...
For nearly 15 years, the biological and biomedical applications of arene ruthenium metalla-assemblies have flourished. Today, the synthetic strategies to generate arene ruthenium assemblies are well-established, and these compounds offer tremendous possibilities in terms of structural diversities and chemical properties. However, the second coordin...
The synthesis and characterization of three metalla-rectangles of the general formula [Ru4(η⁶-p-cymene)4(μ4-clip)2(μ2-Lanthr)2][CF3SO3]4 (Lanthr: 9,10-bis(3,3’-ethynylpyridyl) anthracene; clip = oxa: oxalato; dobq: 2,5-dioxido-1,4-benzoquinonato; donq: 5,8-dioxido-1,4-naphthoquinonato) are presented. The molecular structure of the metalla-rectangle...
A new complex N-(2-hydroxyethylamino)ethylsalicylaldiminato]-palladium(II) chloride [Pd(L)Cl] was synthesized by the reaction in ethanol of the Schiff base 2-(2-(2-hydroxyethylamino)ethylimino)methyl phenol (LH) and Li2PdCl4. The complex was characterized by ¹H NMR, ¹³C NMR, FT-IR and UV–Vis spectroscopic techniques. The structure of the complex wa...
The Schiff-base 5-methyl-4-{(pyridin-2-ylmethylene)amino}-4H-1,2,4-triazole-3-thiol (L-H) reacts in alcoholic solution (methanol, ethanol, isopropanol) at room temperature with the dinuclear precursor [(η⁶-MeC6H4Prⁱ)RuCl2]2 to give a series of neutral complexes of the general formula (η⁶-MeC6H4Prⁱ)Ru(L-OR) (R = Me, 1; R = Et, 2; R = Prⁱ, 3). In the...
Pyridyl-functionalized melamine (MEpy) and barbituric acid (BApy) derivatives have been designed to generate rosette-type structures with multiple coordination sites. The introduction of a pyridyl group on both components (MEpy and BApy) allows coordination of metals at the periphery of the (MEpy)3∙(BApy)3 rosette. Dichloro para-cymene ruthenium an...
NMR chemical profiling of a Laurenciella sp. using a computerized method developed in our laboratory resulted in the identification of five new compounds (1–5) and 17 known compounds, among which 3-(E)-laurenyne represented by far the most abundant metabolite. Compounds 1 to 5 were isolated and fully characterized by detailed spectroscopic analysis...
A series of neutral ruthenium(II)–arene complexes, [(arene)Ru(QR)Cl] (arene = p-cymene or hexamethylbenzene), containing 4-acyl-5-pyrazolonate (QR) ligands with aromatic substituents in the acyl moiety (a phenyl in QPh and a 1-naphthyl in Qnaph) and related ionic complexes [(arene)Ru(QR)(PTA)][PF6] (PTA = 1,3,5-triaza-7-phosphaadamantane) have been...
For many years, the use of arene ruthenium complexes in catalysis and bioinorganic chemistry has showed great promises due to their chemical properties, but opportunities remain in supramolecular chemistry where arene ruthenium units are still poorly exploited. The strength of coordination bonds offers limitless possibilities in the field of supram...
This chapter deals with the design of metal catalysts intercalated in smectite clays and their applications in the field of heterogeneous catalysis. Smectite clay characteristics such as molecular structure, chemical composition, and their properties including ion exchange, acidity, and swelling are discussed to give the necessary background for th...
Because the size is a key element in the development of an enhanced permeability and retention (EPR)-effective drug, we present here our first step in the design of larger and heavier discrete arene ruthenium metallaassemblies. Synthetic strategies, together with the future of these systems in biology, are discussed.
Two imidazo[1,5-a]pyridine-based ligands, namely 2-(1-phenylimidazo[1,5-a]pyridin-3-yl)phenol (N,OH-LPh) and 2-(1-methylimidazo[1,5-a]pyridin-3-yl)phenol (N,OH-LMe) have been reacted with different divalent metals (M = Co, Cu, Ni, Pd) to obtain the following complexes [Co(N,O-LPh)2] (1), [Cu(N,O-LPh)2] (2), [Ni(N,O-LPh)2] (3), [Pd(N,O-LPh)2] (4), [...
A series of half-sandwich pentamethylcyclopentadienyl rhodium(III) and iridium(III) complexes [Cp*M(DBM/HDB/AVB)Cl] and [Cp*M(DBM/HDB/AVB)(PTA)][SO3CF3], where Cp* = pentamethylcyclopentadienyl, the proligands DBMH = dibenzoylmethane, HDBH = o-hydroxydibenzoylmethane, AVBH = avobenzone, and PTA = 1,3,5-triaza-7-phosphaadamantane, is reported. All t...
The mixed ligand copper(I) derivative [Cu(PPh3)2(κ²-O,O″-lact)] (1) (lact = L-(+)-lactate) has been prepared and fully characterized. NMR studies indicated the occurrence of a fluxional behavior involving the lactate anion, in solution. The α-hydroxycarboxylate ligand is responsible for the generation of a catemeric O–H⋯O(CO) H-bonding network that...
Two mononuclear rhodium complexes, Rh(I)- 1,5-cyclooctadiene and Rh(III)- pentamethylcyclopentadienyl, and a bimetallic Rh(I)-Rh(III) mixed-valence complex were synthesised. The complexes were fully characterised using an array of analytical techniques which included NMR and infrared spectroscopy, single-crystal X-ray diffractometry, elemental anal...
The reactivity of the highly cytotoxic complex-in-a-complex cation [Pt(acac)2�(pcym)
6Ru6(tpt)2(dhnq)3]6+ ([Pt(acac)2�1]6+) towards amino acids, proteins, nucleotides and an oligonucleotide
was investigated by NMR, MS, UV/Vis and CD experiments. The similarities and differences
between the metallaprism [Pt(acac)2�1]6+, its empty counterpart [1]6+ a...
A new melamine (ME)–barbituric acid (BA) rosette-type system has been prepared and characterized. The introduction of a pyridyl group on the barbituric acid moiety allows coordination of metal ions at the periphery of the ME3·BA3 rosette. Reactions of 1.5 equiv. of [Ru(cym)Cl2]2 (cym = p-cymene) or [M(Cp*)Cl2]2 (Cp* = pentamethylcyclopentadienyl; M...
Seven mononuclear heteroleptic silver(i) complexes, [Ag(N∩N)(PR3)](NO3) (N∩N = 2-(1-(pyridin-2-yl)imidazo[1,5-a]pyridin-3-yl)phenol; P = PPh3 (1), PMe2Ph (2), PMePh2 (3), P(p-tolyl)3 (4), P(ⁿBu)3 (5), P(OPh)3 (6), and P(OEt)3 (7)), have been prepared and characterized. In these compounds, N∩N acts as a bidentate ligand with the pyridine ring and th...
This book chapter intends to give students and more experienced chemists an overview of the available techniques for studying host–guest systems in solution. Instead of being centered on a specific host or a family of hosts, this book chapter focuses on pyrene, probably the most common and most studied guest in the literature. All standard techniqu...
Organometallic chemistry, like all other fields in chemistry, has reached a level of sophistication that was unthinkable 65 years ago when ferrocene was discovered. The complexity of organometallic compounds has progressed in parallel to the techniques available for their characterization, and nowadays applications are driving the field. While cata...
Three ureido-pyrimidone derivatives (N-LH) were used to generate in combination with four dinuclear arene ruthenium clips, (p-cymene)2Ru2(OO∩OO)Cl2 (OO∩OO = oxalato, 2,5-dioxido-1,4-benzoquinonato, 2,5-dichloro-1,4-benzoquinonato, 5,8-dioxido-1,4-naphtoquinonato), twelve cationic arene ruthenium metalla-cycles of the general formula [(p-cymene)2Ru2...
A series of neutral ruthenium(II) arene complexes [(arene)Ru(QR)Cl] (arene = p-cymene (cym) or hexamethylbenzene (hmb)) containing 4-acyl-5-pyrazolonate QR ligands with different electronic and steric substituents (R = 4-cyclohexyl, 4-stearoyl, or 4-adamantyl) and related ionic complexes [(arene)Ru(QR)(PTA)][PF6] (PTA = 1,3,5-triaza-7-phosphaadaman...
The synthesis of a series of neutral arene ruthenium(II) complexes (arene = p-cymene, hexamethylbenzene and benzene) [(arene)Ru(HDB)Cl] derived from the reaction of the appropriate arene ruthenium(II) dimers and ortho-hydroxydibenzoylmethane (HDBH), a potent inhibitor of cell proliferation, is described. In addition, related ionic complexes [(arene...
The bond between molybdenum and substituted 1,10-phenanthroline ligands in a series of [Mo(CO)4(phen*)] complexes has been studied by combining experimental data (νCO) with DFT calculations. First, natural orbitals for chemical valence (NOCV) were calculated: The resulting charge-transfer magnitudes (Δqi) associated with the deformation density cha...
Recently, a series of thiazolo arene ruthenium complexes were found to be highly cytotoxic in vitro, on both cisplatin-sensitive and cisplatin-resistant ovarian cancer cells. The most active compound of the series, [(η(6)-p-cymene)Ru(L)Cl]Cl (L = 1-(2-(2-(3-chlorobenzylidene)hydrazinyl)-4-methylthiazol-5-yl)ethanone), was selected for an in vivo st...
Four diruthenium trithiolato chlorambucil conjugates have been prepared via Steglich esterification from chlorambucil and the corresponding trithiolato precursors. All conjugates are highly cytotoxic towards human ovarian A2780 and A2780cisR cancer cell lines with IC50 values in the nanomolar range. The conjugates exhibit selectivity towards A2780...
Organic Nanoreactors: From Molecular to Supramolecular Organic Compounds provides a unique overview of synthetic, porous organic compounds containing a cavity which can encapsulate one or more guest(s). Confined space within a nanoreactor can isolate the guest(s) from the bulk and effectively influence the reaction inside the nanoreactor. Naturally...
A series of octanuclear p-cymene ruthenium and pentamethylcyclopentadienyl rhodium and iridium metalla-assemblies has been prepared from tetrapyridyl porphyrin (tpp) panels and the corresponding dinuclear clips, (η6-MeC6H4Pri)2Ru2(μ4-C6HRO4)Cl2 (R = C11H23) and (η5-C5Me5)2M2(μ4-C6HRO4)Cl2 (M = Rh, Ir). All complexes were isolated in good yield as t...
Four complexes of the general formula [(η6-p-Me-C6H4Pri)2-Ru2-(μ-SC2H4R)3]+, R = (CF2)7CF3 (1), (CF2)5CF3 (2), (CF2)3CF3 (3) and (CH2)5CH3 (4) were synthesized and characterised. The molecular structures of complexes 1 and 3 were confirmed by single crystal X-ray diffraction analysis of their chloride salts. Complexes 3 and 4 were evaluated for the...
The hydrogen-bonded arene ruthenium metalla-rectangle, [(p-cymene)2Ru2(OO∩OO)(UPy)2]2(4+), obtained from 1-(4-oxo-6-undecyl-1,4-dihydropyrimidin-2-yl)-3-(pyridin-4-ylmethyl)urea (UPy) and the dinuclear arene ruthenium clip (p-cymene)2Ru2(OO∩OO)Cl2 (OO∩OO = 2,5-dioxido-1,4-benzoquinonato), is investigated by means of solution-phase NMR spectroscopy....
Tetranuclear arene ruthenium complexes of the general formula [{Ru2(p-cymene)2(μ4-L)}2(μ4-tpom)]4+ (tpom = tetrakis(4-pyridyloxymethylene)methane) were obtained from the corresponding dinuclear arene ruthenium complexes [Ru2(p-cymene)2(μ4-L)Cl2] (L = diethyl-1,2-diazenedicarboxylato (dadc), oxalato (oxa), bis(2-hydroxyethyl)oxamidato (bho), bis{2-(...
Association of [60]fullerene with arene ruthenium moieties has been achieved for the first time. Two fullerenopyrrolidine derivatives (N-pyr-C-60) were synthesized via a 1,3-dipolar cycloaddition, and coordinated to arene ruthenium complexes to form two half-sandwich complexes of the general formula (p-cymene)RuCl2(N-pyr-C-60). The coordination of...
Three gold(I) complexes of alkynyl chromones were synthesized and characterized. The single-crystal X-ray structure analysis of a dinuclear compound and of a flavone derivative exhibit a typical d¹⁰ gold(I)-alkynyl linear arrangement. All complexes were evaluated as anticancer and antibacterial agents against four human cancer cell lines and four p...
Sixteen hydrazinyl-thiazolo arene ruthenium complexes of the general formula [(η6-p-cymene)Ru(N,N'-hydrazinyl-thiazolo)Cl]Cl were synthesized. All complexes were tested in vitro for their antiproliferative activity on three tumor cell lines (HeLa, A2780, A2780cisR) and on a non-cancerous cell line (HFL-1). A superior cytotoxic activity of the ruthe...
The molecular structure of the title complex, [Ru2(C8H9OS)2Cl2(C10H14)2]·2CHCl3 or (p-MeC6H4Prⁱ)2Ru2(SCH2-p-C6H5-OCH3)2Cl2·2CHCl3, shows inversion symmetry. The two symmetry-related RuII atoms are bridged by two 4-methoxy-α-toluenethiolato [(4-methoxyphenyl)methanethiolato] units. One chlorido ligand and the p-cymene ligand complete the ty...
The crystal structure of the dinuclear arene ruthenium title complex, [Ru2(C6H5OS)(C7H7S)2(C10H14)2]BF4, shows the two RuII atoms to be bridged by two benzylthiophenolate units and one 4-hydroxythiophenolate unit, with the remaining three coordination sites of each RuII atom being occupied by p-cymene ligands, completing the typical piano-st...
Three neutral dinuclear p-cymene ruthenium complexes (1a−1c) of the general formula (p-cyme-ne) 2 Ru 2 (μ 4-L)Cl 2 , bridged by substituted hydroxybenzoqui-nonato spacers (L a = 2,5-dihydroxy-3-phenyl-1,4-benzoquino-nato; L b = 2,5-dihydroxy-3,6-diphenyl-1,4-benzoquinonato; L c = 2,5-dihydroxy-3,6-(3,5-dimethylphenyl)-1,4-benzoquinona-to) have been...
A convenient synthesis of ferrocenyl-4-thiothymine-3,6-dihydro-2H-thiopyrane (3) and ferrocenyl-thymine-3,6-dihydro-2H-thiopyrane (4) by a hetero-Diels-Alder cycloaddition reaction is reported. These complexes represent new class of ferrocenyl nucleobase derivatives. The 2H-thiopyrane ring mimics the sugar subunit present in natural nucleosides and...
A new series of cationic dinuclear arene ruthenium complexes bridged by three thiophenolato ligands, [(h 6-arene) 2 Ru 2 (m 2-SR) 3 ] þ with arene ¼ indane, R ¼ met: 1 (met ¼ 4-methylphenyl); R ¼ mco: 4 (mco ¼ 4-methylcoumarin-7-yl); arene ¼ biphenyl, R ¼ met: 2; R ¼ mco: 5; arene ¼ 1,2,3,4-tetrahydronaphthalene, R ¼ met: 3; R ¼ mco: 6, have been p...
Two pentamethylcyclopentadienyl (Cp*) rhodium(III) and iridium(III) metalla-prisms of the general formula [(Cp*M)6(tpt)2(dhnq)3]6+ (tpt = 2,4,6-tri-(pyridin-4-yl)-1,3,5-triazine, dhnq = 5,8-dihydroxy-1,4-naphthoquinonato; M = Rh, [1]6+; M = Ir, [2]6+) have been synthesized by mixing in methanol the neutral dinuclear complexes (Cp*M)2(dhnq)Cl2 (M =...
Three novel diferrocenyl complexes were prepared and characterised. 2,2-Diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran (, sulphide) was accessible by the hetero-Diels-Alder reaction of diferrocenyl thioketone with 2,3-dimethyl-1,3-butadiene. Stepwise oxidation of gave the respective oxides 2,2-diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran-...
The title compound, [Ir(η⁵-C5Me5)Cl(C18H14ClN3)]B(C6H5)4, is chiral at the metal center and crystallizes as a racemate. In the cation, the hydrazinylidenepyridine ligand is N,N-coordinated through the N-pyridyl and N-hydrazinylidene groups forming a five-membered metallacycle. An intramolecular C—H⋯Cl hydrogen bond is observed. In the crystal,...
The cation of the title compound, [Rh(η⁵-C5Me5)Cl(C13H12ClN3)]Cl, adopts a typical piano-stool geometry. The complex is chiral at the metal and crystallizes as a racemate. Upon coordination, the hydrazinylidenepyridine ligand is non-planar, an angle of 54.42 (7)° being observed between the pyridine ring and the aromatic ring of the [2-(4-chlorop...
Interactions between three hexacationic arene ruthenium metallaprisms, ([(p-cymene)6Ru6(tpt)2(dhnq)3]6+, [(p-cymene)6Ru6(tpt)2(dhbq)3]6+ and [(p-cymene)6Ru6(tpt)2(oxa)3]6+, and a series of human proteins including human serum albumin, transferrin, cytochrome c, myoglobin and ubiquitin have been studied using NMR spectroscopy, mass spectrometry and...
The monothiolato complexes [(η6-p-MeC6H4iPr)2Ru2Cl2(μ-Cl)(μ-SR)] with R = CH2C6H5 (1), p-CH2C6H4NO2 (2), C10H15 (3), m-9-B10C2H11 (4) were synthesized by treating [(η6-p-MeC6H4iPr)2Ru2Cl2(μ-Cl)2] with the corresponding thiols RSH. The reaction of p-cymene ruthenium dichloride dimer with thiols is well known to give the cationic trithiolato complexe...
New and known arylidene-hydrazinyl-thiazole derivatives have been synthesized by a convenient Hantzsch condensation. All compounds were evaluated for their in vitro cytotoxicity on two carcinoma cell lines, MDA-MB231 and HeLa. Significant antiproliferative activity for 2-(2-benzyliden-hydrazinyl)-4-methylthiazole on both MDA-MB-231 (IC50: 3.92 µg/m...
New and known arylidene-hydrazinyl-thiazole derivatives have been synthesized by a convenient Hantzsch condensation. All compounds were evaluated for their in vitro cytotoxicity on two carcinoma cell lines, MDA-MB231 and HeLa. Significant antiproliferative activity for 2-(2-benzyliden-hydrazinyl)-4-methylthiazole on both MDA-MB-231 (IC50: 3.92 µg/m...
Arene ruthenium complexes are known for 50 years and the number of publications involving arene ruthenium complexes is in constant progression ever since their discovery. Following the synthesis and characterisation of the first arene ruthenium complexes, they have been initially tested as catalysts. Then later on, with the emergence of bio-inorgan...
The association of the arene ruthenium metalla-cycle [Ru4(p-cymene)4(bpe)2(donq)2][DOS]4 (bpe = 1,2-bis(4-pyridyl)ethylene, donq = 5,8-dioxydo-1,4-naphtoquinonato, DOS = dodecyl sulfate) with pyrenyl-functionalized poly(arylester) dendrimers bearing cyanobiphenyl end-groups is reported. The supramolecular dendritic systems display mesomorphic prope...