Search Results (20)

The incorporation of transition metal atoms into [Ge₉] clusters is a widely studied area of Zintl-cluster chemistry. Recently, it was shown that clusters comprising single transition metal atoms in the cluster surface show catalytic properties. Here, we present a synthetic approach to four new compounds comprising silylated Ge₉ clusters with organometallic ruthenium complexes. [η⁵-Ge₉Hyp₃]RuCp* (1), [η¹-Ge₉(Si^tBu₂H)₃]RuCp(PPh₃)₂ (2), and [Hyp₃Ge₉][RuCp(PPh₃)₂(MeCN)] (3b) (Cp = cyclopentadienyl, Cp* = pentamethylcyclopentadienyl, Hyp = Si(SiMe₃)₃, Ph = C₆H₅, ^tBu = tert-butyl) were characterized by means of NMR spectroscopy and single-crystal structure determination. In the case of 2, a new isomer with an approximated C_4v symmetric monocapped square antiprism of nine Ge atoms with an unexpected ligand arrangement comprising three ditertbutylsilane ligands attached to the open square was obtained. [Hyp₃Ge₉][RuCp(PPh₃)₂] (3a) was characterized via NMR spectroscopy and LIFDI mass spectrometry. Overall, we were able to show that the steric demand of the ligands Cp vs. Cp* and hypersilylchloride vs. ditertbutylsilane strongly influence the arrangement of the atoms and ligands on the cluster. In addition, the solvent also affects the cluster, as it appears that the ruthenium atom in 3a dissociates from the cluster surface upon acetonitrile coordination to form 3b. These results show that choosing the right synthetic tools and ligands makes a big difference in the outcome of the metalation reaction. Full article

A one-pot, one-step protocol combining hydrogen transfer initiated dehydration (HTID) of 1,3-propanediol (1,3-PDO), catalysed by [Cp*IrCl₂(NHC)] (Cp* = pentamethylcyclopentadienyl; NHC = carbene ligand) complexes (1-5H and 1-3F), and self-aldol condensation (SAC) of propanal (2), allowed selective production of C6 aldehyde 2-methyl-pent-2-enal (3), in ionic liquids with high substrate conversion. This shows, for the first time, the conversion of 1,3-propanediol to C6 aldehydes in one pot via a catalytic hydrogen borrowing methodology. The Ir(III) pre-catalysts and the ionic liquids were recyclable. C6 aldehyde 2-methyl-pent-2-enal could also be selectively produced in the presence of water and in neat 1,3-PDO. The efficient, selective delivery of a value-added chemical from 1,3-PDO, a major product of many whole-cell bacterial fermentation processes, shows that the combination of chemo-catalytic processing of the chemical platform via Cp*IrCl₂(NHC)-catalysed HTID/SAC with bio-catalysis has the potential to allow direct valorisation of the bio-renewable feedstocks, such as waste glycerol and sugars, into valuable chemicals. Full article

The (pentamethylcyclopentadienyl)chloridoiridium(III) complex bearing a κP,κS-bonded Ph₂PCH₂CH₂SPh ligand ([Ir(η⁵-C₅Me₅)Cl(Ph₂P(CH₂)₂SPh-κP,κS)]PF₆, (1)] was synthesized and characterized. Multinuclear (¹H, ¹³C and ³¹P) NMR spectroscopy was employed for the determination of the structure. Moreover, SC-XRD confirmed the proposed structure belongs to the “piano stool” type. The Hirshfeld surface analysis outlined the most important intermolecular interactions in the structure. The crystallographic structure was optimized at the B3LYP-D3BJ/6-311++G(d,p)(H,C,P,S,Cl)/LanL2DZ(Ir) level of theory. The applicability of this level was verified through a comparison of experimental and theoretical bond lengths and angles, and ¹H and ¹³C NMR chemical shifts. The Natural Bond Orbital theory was used to identify and quantify the intramolecular stabilization interactions, especially those between donor atoms and Ir(III) ions. Complex 1 was tested on antitumor activity against five human tumor cell lines: MCF-7 breast adenocarcinoma, SW480 colon adenocarcinoma, 518A2 melanoma, 8505C human thyroid carcinoma and A253 submandibular carcinoma. Complex 1 showed superior antitumor activity against cisplatin-resistant MCF-7, SW480 and 8505C cell lines. The mechanism of tumoricidal action on 8505C cells indicates the involvement of caspase-induced apoptosis, accompanied by a considerable reduction in ROS/RNS and proliferation potential of treated cells. Full article

Organic amines are important compounds present in a wide variety of products, which makes the development of new systems for their detection an interesting field of study. New organometallic complexes of group 9 [MCp*X(2′-R-2-py-SBF)] (M = Ir, Rh; R = H, X = Cl (6), R = H, X = OAc (7), R = CHO, X = Cl (8)), and [IrCp*Cl(2′, 7-diCHO-2-py-SBF)] (9) (Cp* pentamethylcyclopentadienyl, SBF = 9,9’-spirobifluorene) bearing bidentate C–N ligands based on 9,9′-spirobifluorene were obtained and characterized by NMR spectroscopy, mass spectrometry, IR spectroscopy, and X-ray diffraction analysis when possible. The formation of a Schiff base to give complexes with the formula [MCp*Cl(2′-CH=NR-2-py-SBF)] (M = Ir, Rh; R = alkyl or aryl (10–12)), through condensation of an amine, and the aldehyde group present in these new complexes was studied leading to a selective reactivity depending on the nature of the amine and the metal center. While the iridium complexes only react with aromatic amines, the rhodium derivative requires heat for those but can react at room temperature with aliphatic amines. Full article

Chiral diamines based on an 8-amino-5,6,7,8-tetrahydroquinoline backbone, known as CAMPY (L1), or the 2-methyl substituted analogue Me-CAMPY (L2) were employed as novel ligands in Cp* metal complexes for the ATH of a series of substituted dihydroisoquinolines (DHIQs), known for being key intermediates in the synthesis of biologically active alkaloids. Different metal-based complexes were evaluated in this kind of reaction, rhodium catalysts, C3 and C4, proving most effective both in terms of reactivity and enantioselectivity. Although modest enantiomeric excess values were obtained (up to 69% ee in the case of substrate I), a satisfactory quantitative conversion was successfully fulfilled even in the case of the most demanding hindered substrates when La(OTf)₃ was used as beneficial additive, opening up the possibility for a rational design of novel chiral catalysts alternatives to the Noyori-Ikariya (arene)Ru(II)/TsDPEN catalyst. Full article

The pH-dependent binding strengths and modes of the organometallic [(η⁶-p-cym)M(H₂O)₃]²⁺ (M^II = Ru, Os; p-cym = 1-methyl-4-isopropylbenzene) or [(η⁵-Cp*)M(H₂O)₃]²⁺ (M^III = Rh, Ir; Cp* = pentamethylcyclopentadienyl anion) cations towards iminodiacetic acid (H₂Ida) and its biorelevant mono- and diphosphonate derivatives N-(phosphonomethyl)-glycine (H₃IdaP) and iminodi(methylphosphonic acid) (H₄Ida2P) was studied in an aqueous solution. The results showed that all three of the ligands form 1:1 complexes via the tridentate (O,N,O) donor set, for which the binding mode was further corroborated by the DFT method. Although with IdaP³⁻ and Ida2P⁴⁻ in mono- and bis-protonated species, where H⁺ might also be located at the non-coordinating N atom, the theoretical calculations revealed the protonation of the phosphonate group(s) and the tridentate coordination of the phosphonate ligands. The replacement of one carboxylate in Ida²⁻ by a phosphonate group (IdaP³⁻) resulted in a significant increase in the stability of the metal complexes; however, this increase vanished with Ida2P⁴⁻, which was most likely due to some steric hindrance upon the coordination of the second large phosphonate group to form (5 + 5) joined chelates. In the phosphonate-containing systems, the neutral 1:1 complexes are the major species at pH 7.4 in the millimolar concentration range that is supported by both NMR and ESI-TOF-MS. Full article

Two novel phosphine ligands, Ph₂PCH₂N(CH₂CH₃)₃ (1) and Ph₂PCH₂N(CH₂CH₂CH₂CH₃)₂ (2), and six new metal (Cu(I), Ir(III) and Ru(II)) complexes with those ligands: iridium(III) complexes: Ir(η5-Cp*)Cl₂(1) (1a), Ir(η5-Cp*)Cl₂(2) (2a) (Cp*: Pentamethylcyclopentadienyl); ruthenium(II) complexes: Ru(η6-p-cymene)Cl₂(1) (1b), Ru(η6-p-cymene)Cl₂(2) (2b) and copper(I) complexes: [Cu(CH₃CN)₂(1)BF₄] (1c), [Cu(CH₃CN)₂(2)BF₄] (2c) were synthesized and characterized using elemental analysis, NMR spectroscopy, and ESI-MS spectrometry. Copper(I) complexes turned out to be highly unstable in the presence of atmospheric oxygen in contrast to ruthenium(II) and iridium(III) complexes. The studied Ru(II) and Ir(III) complexes exhibited promising cytotoxicity towards cancer cells in vitro with IC₅₀ values significantly lower than that of the reference drug—cisplatin. Confocal microscopy analysis showed that Ru(II) and Ir(III) complexes effectively accumulate inside A549 cells with localization in cytoplasm and nuclei. A precise cytometric analysis provided clear evidence for the predominance of apoptosis in induced cell death. Furthermore, the complexes presumably induce the changes in the cell cycle leading to G2/M phase arrest in a dose-dependent manner. Gel electrophoresis experiments revealed that Ru(II) and Ir(III) inorganic compounds showed their unusual low genotoxicity towards plasmid DNA. Additionally, metal complexes were able to generate reactive oxygen species as a result of redox processes, proved by gel electrophoresis and cyclic voltamperometry. In vitro cytotoxicity assays were also carried out within multicellular tumor spheroids and efficient anticancer action on these 3D assemblies was demonstrated. It was proven that the hydrocarbon chain elongation of the phosphine ligand coordinated to the metal ions does not influence the cytotoxic effect of resulting complexes in contrast to metal ions type. Full article

A new catalytic system has been developed for hydrogen production from various monosaccharides, mainly glucose, as a starting material under reflux conditions in water in the presence of a water-soluble dicationic iridium complex bearing a functional bipyridine ligand. For example, the reaction of D-glucose in water under reflux for 20 h in the presence of [Cp*Ir(6,6′-dihydroxy-2,2′-bipyridine)(H₂O)][OTf]₂ (1.0 mol %) (Cp*: pentamethylcyclopentadienyl, OTf: trifluoromethanesulfonate) resulted in the production of hydrogen gas in 95% yield. In the present catalytic reaction, it was experimentally suggested that dehydrogenation of the alcoholic moiety at 1-position of glucose proceeded. Full article

Piano-stool iridium complexes based on the pentamethylcyclopentadienyl ligand (Cp*) have been intensively investigated as anticancer drug candidates and hold much promise in this setting. A systematic study aimed at outlining the effect of Cp* mono-derivatization on the antiproliferative activity is presented here. Thus, the dinuclear complexes [Ir(η⁵-C₅Me₄R)Cl(μ-Cl)]₂ (R = Me, 1a; R = H, 1b; R = Pr, 1c; R = 4-C₆H₄F, 1d; R = 4-C₆H₄OH, 1e), their 2-phenylpyridyl mononuclear derivatives [Ir(η⁵-C₅Me₄R)(k_N,k_CPhPy)Cl] (2a–d), and the dimethylsulfoxide complex [Ir{η⁵-C₅Me₄(4-C₆H₄OH)}Cl₂(κ_S-Me₂S=O)] (3) were synthesized, structurally characterized, and assessed for their cytotoxicity towards a panel of six human and rodent cancer cell lines (mouse melanoma, B16; rat glioma, C6; breast adenocarcinoma, MCF-7; colorectal carcinoma, SW620 and HCT116; ovarian carcinoma, A2780) and one primary, human fetal lung fibroblast cell line (MRC5). Complexes 2b (R = H) and 2d (4-C₆H₄F) emerged as the most active ones and were selected for further investigation. They did not affect the viability of primary mouse peritoneal cells, and their tumoricidal action arises from the combined influence on cellular proliferation, apoptosis and senescence. The latter is triggered by mitochondrial failure and production of reactive oxygen and nitrogen species. Full article

Two novel, pyridinone-based chelating ligands containing separated (O,O) and (N_amino,N_het) chelating sets (N_amino = secondary amine; N_het = pyrrole N for H(L3) (1-(3-(((1H-pyrrole-2-yl)methyl)-amino)propyl)-3-hydroxy-2-methylpyridin-4(1H)-one) or pyridine N for H(L5) (3-hydroxy-2-methyl-1-(3-((pyridin-2-ylmethyl)amino)propyl)pyridin-4(1H)-one)) were synthesized via reduction of the appropriate imines. Their proton dissociation processes were explored, and the molecular structures of two synthons were assessed by X-ray crystallography. These ambidentate chelating ligands are intended to develop Co(III)/PGM (PGM = platinum group metal) heterobimetallic multitargeted complexes with anticancer potential. To explore their metal ion binding ability, the interaction with Pd(II), [(η⁶-p-cym)Ru]²⁺ and [(η⁵-Cp*)Rh]²⁺ (p-cym = 1-methyl-4-isopropylbenzene, Cp* = pentamethyl-cyclopentadienyl anion) cations was studied in aqueous solution with the combined use of pH-potentiometry, NMR and HR ESI-MS. In general, organorhodium was found to form more labile complexes over ruthenium, while complexation of the (N,N) chelating set was slower than the processes of the pyridinone unit with (O,O) coordination. Formation of the organoruthenium complexes starts at lower pH (higher thermodynamic stabilities of the corresponding complexes) than for [(η⁵-Cp*)Rh]²⁺ but, due to the higher affinity of [η⁶-p-cym)Ru]²⁺ towards hydrolysis, the complexed ligands are capable of competing with hydroxide ion in a lesser extent than for the rhodium systems. As a result, under biologically relevant conditions, the rhodium binding effectivity of the ligands becomes comparable or even slightly higher than their effectivity towards ruthenium. Our results indicate that H(L3) is a less efficient (N,N) chelator for these metal ions than H(L5). Similarly, due to the relative effectivity of the (O,O) and (N,N) chelates at a 1:1 metal-ion-to-ligand ratio, H(L5) coordinates in a (N,N) manner to both cations in the whole pH range studied while, for H(L3), the complexation starts with (O,O) coordination. At a 2:1 metal-ion-to-ligand ratio, H(L3) cannot hinder the intensive hydrolysis of the second metal ion, although a small amount of 2:1 complex with [(η⁵-Cp*)Rh]²⁺ can also be detected. Full article

Rhodium is one of the most used metals in catalysis both in laboratory reactions and industrial processes. Despite the extensive exploration on “classical” ligands carried out during the past decades in the field of rhodium-catalyzed reactions, such as phosphines, and other common types of ligands including N-heterocyclic carbenes, ferrocenes, cyclopentadienyl anion and pentamethylcyclopentadienyl derivatives, etc., there is still lively research activity on this topic, with considerable efforts being made toward the synthesis of new preformed rhodium catalysts that can be both efficient and selective. Although the “golden age” of homogeneous catalysis might seem over, there is still plenty of room for improvement, especially from the point of view of a more sustainable chemistry. In this review, temporally restricted to the analysis of literature during the past five years (2015–2020), the latest findings and trends in the synthesis and applications of Rh(I) complexes to catalysis will be presented. From the analysis of the most recent literature, it seems clear that rhodium-catalyzed processes still represent a stimulating challenge for the metalloorganic chemist that is far from being over. Full article

Ru^II(cym)Cl (cym = η⁶-p-cymene) complexes of pyridinecarbothioamides have shown potential for development as orally active anticancer metallodrugs, underlined by their high selectivity towards plectin as the molecular target. In order to investigate the impact of the metal center on the anticancer activity and their physicochemical properties, the Os(cym), Rh- and Ir(Cp*) (Cp* = pentamethylcyclopentadienyl) analogues of the most promising and orally active compound plecstatin 2 were prepared and characterized by spectroscopic techniques and X-ray diffraction analysis. Dissolution in aqueous medium results in quick ligand exchange reactions; however, over time no further changes in the ¹H NMR spectra were observed. The Rh- and Ir(Cp*) complexes were investigated for their reactions with amino acids, and while they reacted with Cys, no reaction with His was observed. Studies on the in vitro anticancer activity identified the Ru derivatives as the most potent, independent of their halido leaving group, while the Rh derivative was more active than the Ir analogue. This demonstrates that the metal center has a significant impact on the anticancer activity of the compound class. Full article

Thiones have been investigated as ligands in metal complexes with catalytic and biological activity. We report the synthesis, characterization, and biological evaluation of a series of M^II/III complexes of the general formulae [M^II(cym)(L)Cl]X (cym = η⁶-p-cymene) or [M^III(Cp*)(L)Cl]X (Cp* = η⁵-pentamethylcyclopentadienyl), where X = Cl⁻ or PF₆⁻, and L represents heterocyclic derivatives of thiourea. The thiones feature a benzyl-triazolyl pendant and they act as bidentate ligands via N,S-coordination to the metal centers. Several derivatives have been investigated by single-crystal X-ray diffraction analysis. NMR investigations showed a counterion-dependent shift of several protons due to the interaction with the counterions. These NMR investigations were complemented with X-ray diffraction analysis data and the effects of different counterions on the secondary coordination sphere were also investigated by DFT calculations. In biological studies, the Ir benzimidazole derivative was found to accumulate in the cytoplasm and it was the most cytotoxic derivative investigated. Full article

Synthesis and reactivities of a new mononuclear hydroxidoiridium(III) complex with a pentamethylcyclopentadienyl (Cp*) ligand are reported. The hydroxido ligand was introduced into an iridium complex having a nonprotic amine chelate derived from N-mesyl-N’,N’-dimethylethylenediamine by substitution of the chloride ligand using KOH. The resulting hydroxidoiridium complex was characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. The hydroxido complex was able to deprotonate benzamide and acetonitrile, and showed an ability to accept a hydride from 2-propanol to generate the corresponding hydrido complex quantitatively. In the reaction with mandelonitrile, a cyanide anion was transferred to the iridium center in preference to the hydride transfer. The cyanidoiridium complex was also identified in the reaction with acetone cyanohydrin, and could serve as catalyst species in the transfer hydrocyanation of benzaldehyde. Full article

As previously shown for lutetium and yttrium, 1,2,3,4,5-pentamethylcyclopentadienyl (C₅Me₅ = Cp*)-bearing rare-earth metal dimethyl half-sandwich complexes [Cp*LnMe₂]₃ are now also accessible for holmium, dysprosium, and terbium via tetramethylaluminato cleavage of [Cp*Ln(AlMe₄)₂] with diethyl ether (Ho, Dy) and tert-butyl methyl ether (TBME) (Tb). C–H-bond activation and ligand redistribution reactions are observed in case of terbium and are dominant for the next larger-sized gadolinium, as evidenced by the formation of mixed methyl/methylidene clusters [(Cp*Ln)₅(CH₂)(Me)₈] and metallocene dimers [Cp*₂Ln(AlMe₄)]₂ (Ln = Tb, Gd). Applying TBME as a “cleaving” reagent can result in both TBME deprotonation and ether cleavage, as shown for the formation of the 24-membered macrocycle [(Cp*Gd)₂(Me)(CH₂OtBu)₂(AlMe₄)]₄ or monolanthanum complex [Cp*La(AlMe₄){Me₃Al(CH₂)OtBu}] and monoyttrium complex [Cp*Y(AlMe₄)(Me₃AlOtBu)], respectively. Complexes [Cp*Ln(AlMe₄)₂] (Ln = Ho, Dy, Tb, Gd) and [Cp*LnMe₂]₃ (Ln = Ho, Dy) are applied in isoprene and 1,3-butadiene polymerization, upon activation with borates [Ph₃C][B(C₆F₅)₄] and [PhNHMe₂][B(C₆F₅)₄], as well as borane B(C₆F₅)₃. The trans-directing effect of AlMe₃ in the binary systems [Cp*Ln(AlMe₄)₂]/borate is revealed and further corroborated by the fabrication of high-cis-1,4 polybutadiene (97%) with “aluminum-free” [Cp*DyMe₂]₃/[Ph₃C][B(C₆F₅)₄]. The formation of multimetallic active species is supported by the polymerization activity of pre-isolated cluster [(Cp*Ho)₃Me₄(CH₂)(thf)₂]. Full article