Diruthenium(II, III) complexes of ibuprofen,aspirin, naproxen and indomethacin non-steroidal anti-inflammatory drugs: Synthesis,characterization and their effects on tumor-cell proliferation

[Ru₂(dNSAID)₄Cl] and novel [Ru₂(dNSAID)₄(H₂O)₂]PF₆ complexes, where dNSAID = deprotonated carboxylate from the non-steroidal anti-inflammatory drugs (NSAIDs), respectively: ibuprofen, Hibp (1) and aspirin, Hasp (2); naproxen, Hnpx (3) and indomethacin, Hind (4), have been prepared and characterized by optical spectroscopic methods. All of the compounds exhibit mixed valent Ru₂(II, III) cores where metal–metal bonds are stabilized by four drug-carboxylate bridging ligands in paddlewheel type structures. The diruthenium complexes and their parent NSAIDs showed no significant effects for Hep2 human larynx or T24/83 human bladder tumor. In contrast, the coordination of Ru₂(II, III) core led to synergistic effects that increased significantly the inhibition of C6 rat glioma proliferation in relation to the organic NSAIDs naproxen and ibuprofen. The possibility that the complexes Ru₂-ibp and Ru₂-npx may exert effects (anti-angiogenic and anti-matrix metalloprotease) that are similar to those exhibited by NAMI-A opens new horizons for in vivo C6 glioma model studies.     

Magnetic properties and magnetic structures of CeAl and PrAla (PrAl annealed)

The intermetallic compounds CeAl and PrAl_a (PrAl annealed) crystallize in the Cmcm orthorhombic space group. They exhibit a metamagnetic behavior below their Néel temperatures. Both compounds have the same noncollinear magnetic structure; rare earth atoms are divided into two sublattices with different magnetization axes which make the same angle with the b axis. Inside each sublattice the arrangement of the moments is collinear and antiferromagnetic. We show that the two moment directions are essentially due to the crystal field effects which act on the rare earth ions lying in a low symmetry site.     

A Diruthenium Complex of an N-Pyridyl-o-aminophenol Derivative: A Route to Mixed Valency

An N-pyridyl-o-aminophenol derivative that stabilises mixed-valence states of ruthenium ions is disclosed. A diruthenium complex, [(L_IQ⁰)Ru₂Cl₅] ⋅ MeOH ( 1⋅ MeOH) is successfully isolated, in which L_IQ⁰ is the o-iminobenzoquinone form of 2-[(3-nitropyridin-2-yl)amino]phenol (L_APH₂). In 1 , L_IQ⁰ oriented towards one ruthenium centre is a non-innocent NO-donor redox ligand, whereas another oriented towards another ruthenium centre is an innocent pyridine-donor redox ligand. Complex 1 is a diruthenium(II,III) mixed-valence complex, [Ru^II(L_IQ⁰)(μ-Cl)₂Ru^III], with a minor contribution from the diruthenium(III,III) state. [Ru^III(L_ISQ^.−)(μ-Cl)₂Ru^III] contains L_ISQ^.−, which is the o-iminobenzosemiquinonate anion radical form of the ligand. Complexes 1 ⁻ and 1 ⁺ are diruthenium(II,II), [Ru^II(L_IQ⁰)(μ-Cl)₂Ru^II], and diruthenium(III,III), [Ru^III(L_IQ⁰)(μ-Cl)₂Ru^III], complexes, respectively, of L_IQ⁰. Complex 1 ²⁻ is a diruthenium(II,II) complex of the o-iminobenzosemiquinonate anion radical (L_ISQ^.−), [Ru^II(L_ISQ^.−)(μ-Cl)₂Ru^II], with a minor contribution from the diruthenium(III,II) form, [Ru^III(L_AP²⁻)(μ-Cl)₂Ru^II]. Complex 1 ²⁺ is a diruthenium(III,IV) mixed-valence complex of L_IQ⁰, [Ru^III(L_IQ⁰)(μ-Cl)₂Ru^IV]. Complexes 1 and 1 ²⁺ exhibit inter-valence charge-transfer transitions at λ=1300 and 1370 nm, respectively.     

Synthesis, structure and electrochemistry of cationic diruthenium complexes of the type [(N∩N)2Ru2(CO)2(μ-CO)2(μ-OOCFc)] containing a ferrocenecarboxylato bridge and two chelating aromatic diimine ligands

The dinuclear bis(ferrocenecarboxylato) complex Ru₂(CO)₄(μ-OOCFc)₂(py)₂ (Fc = ferrocenyl, py = pyridine) was found to react with aromatic diimines (2,2′-dipyridyl, 4,4′-dimethyl-2,2′-dipyridyl, 1,10-phenanthroline, 5-nitro-1,10-phenanthroline, and 5-amino-1,10-phenanthroline) in methanol to give the cationic diruthenium complexes [(N∩N)₂Ru₂(CO)₂(μ-CO)₂(μ-OOCFc)]⁺ (1: N∩N = 2,2′-dipyridyl, 2: N∩N = 4,4′-dimethyl-2,2′-dipyridyl, 3: N∩N = 1,10-phenanthroline, 4: N∩N = 5-nitro-1,10-phenanthroline, 5: N∩N = 5-amino-1,10-phenanthroline), which have been isolated as the hexafluorophosphate salts. The molecular structure of 3, solved by single-crystal X-ray analysis of the tetraphenylborate salt [3][BPh₄], shows a diruthenium backbone bridged by two carbonyl and by one ferrocenecarboxylato ligand, the two 1,10-phenanthroline ligands being in the axial positions. Cyclic voltammetry in dichloromethane reveals for all compounds two successive oxidations due to ferrocene/ferrocenium redox couple and oxidation of the diruthenium core.     

Controlling the electronic density of the [Ru2(DPhF)3(O2CR)] core to obtain one-dimensional compounds

The substitution of the acetate ligand in [Ru₂Cl(DPhF)₃(O₂CMe)] (DPhF⁻ = N,N′-diphenylformamidinate) by the pentafluorobenzoate group gives the complex [Ru₂Cl(DPhF)₃(O₂CC₆F₅)(OH₂)] (1), and the reaction of 1 with AgSO₃CF₃ leads to the compound [Ru₂(DPhF)₃(O₂CC₆F₅)(OH₂)₂]SO₃CF₃ (2). The low donor character of the pentafluorobenzoate ligand compared to the acetate group decreases the electron density of the Ru₂⁵⁺ unit which permits ligands to bond at both axial positions of the diruthenium moiety. The use of the [Au(CN)₂]⁻ group yields the new complex {[Ru₂(DPhF)₃(O₂CC₆F₅)][Au(CN)₂]} (3). Complexes 1–3 are characterized by elemental analysis, ¹⁹F{¹H} NMR, IR and electronic spectroscopy, mass spectrometry and variable-temperature magnetic measurements. The crystal structure of 2·H₂O is also reported. The magnetic properties of complex 1 is in accordance with the ground-state configuration σ²π⁴δ²(π*δ*)³. In contrast, the slope of representation of the magnetic moment towards temperature in complex 2 indicates a gradual transition from essentially high spin (S = 3/2) to low spin (S = 1/2) configuration.     

Synthesis, structure and optical limiting properties of organoruthenium-chalcogenide clusters

Treatment of Ru₃(CO)₁₂ with Ph₃PS affords the compounds [Ru₃(μ₃-S)₂(CO)_9 − n(PPh₃)_n] (n = 1 (1a), 2 (2a)) and [Ru₃(μ₃-S)(μ₃-CO)(CO)₇(PPh₃)₂] (3a) as the major products. Single crystal X-ray diffraction studies of [Ru₃(μ₃-S)₂(CO)₈(PPh₃)] and [Ru₃(μ₃-S)(μ₃-CO)(CO)₇(PPh₃)₂] show these two classes of compounds to contain square pyramidal Ru₃S₂ and trigonal pyramidal Ru₃S metal cores, respectively, with the latter being isostructural to the analogous selenide cluster compound. The clusters [Ru₃(μ₃-E)₂(CO)_9 − n(PPh₃)_n] (E = S, n = 1; E = Se, n = 2) readily undergo ligand displacement reactions with PPh₃ to afford the compounds [Ru₃(μ₃-E)₂(CO)₆(PPh₃)₃] (E = S, 5a; E = Se 5b). The mixed chalcogenide cluster, [Ru₃(μ₃-S)(μ₃-Se)(CO)₇(PPh₃)₂] (6), was prepared from the reaction of [Ru₃(μ₃-S)(μ₃-CO)(CO)₇(PPh₃)₂] and SePPh₃. The optical limiting properties of the complexes 1a,b, 2a,b, 5a,b have been measured by the Z-scan technique employing 40 ns pulses at 523 nm; power limiting was observed for all clusters under our experimental conditions.     

Metamagnetic transition in the 75 K antiferromagnet Gd4Co2Mg3

Gd₄Co₂Mg₃ (Nd₄Co₂Mg₃ type; space group P2/m; a=754.0(4), b=374.1(1), c=822.5(3) pm and β=109.65(4)° as unit cell parameters) was synthesized from the elements by induction melting in a sealed tantalum tube. Its investigation by electrical resistivity, magnetization and specific heat measurements reveals an antiferromagnetic ordering at T_N=75(1) K. Moreover, this ternary compound presents a metamagnetic transition at low critical magnetic field (H_cr=0.93(2) T at 6 K) and exhibits a magnetic moment of 6.3(1) μ_B per Gd-atom at 6 K and H=4.6 T. Due to this transition the compound shows a moderate magnetocaloric effect; at 77 K the maximum of the magnetic entropy change is ΔS_M=−10.3(2) J/kg K for a field change of 0-4.6 T. This effect is compared to that reported previously for compounds exhibiting a magnetic transition in the same temperature range.     

Effect of the synthesis conditions on the magnetic and electrical properties of the BaFeO3−x oxide: A metamagnetic behavior

The BaFeO_2.95 oxide has been obtained from thermal decomposition of the [BaFe(C₃H₂O₄)₂(H₂O)₄] metallo-organic precursor at 800 °C under atmospheric oxygen pressure as small and homogeneous particles. From electronic paramagnetic resonance data, a metallic behavior in the 230-130 K temperature range has been observed. Magnetic measurements confirm the existence of a ferro-antiferromagnetic transition at 178 K. The magnetic properties of the BaFeO_2.95 oxide are strongly dependent on both temperature and magnetic field with a metamagnetic behavior. The synthesis conditions play an important role on the morphology and the electrical and magnetic properties. The syntherization of the sample produces a dramatic change in the transport properties and the existence of conductivity disappears.     

IR,Raman, and Surface‐enhanced Raman Spectroscopic Study on Triruthenium Dipyridylamide Diruthenium Nickel Dipyridylamide Family: Metal‐metal Bonding and Structures

We report the infrared, Raman, and surface‐enhanced Raman scattering (SERS) spectra of triruthenium dipyridylamido complexes and of diruthenium mixed nickel metal‐string complexes. From the results of analysis on the vibrational modes, we assigned their vibrational frequencies and structures. The infrared band at 323–326 cm^?1 is assigned to the Ru₃ asymmetric stretching mode for [Ru₃(dpa)₄Cl₂]^0–2+. In these complexes we observed no Raman band corresponding to the Ru₃ symmetric stretching mode although this mode is expected to have substantial Raman intensity. There is no frequency shift in the Ru₃ asymmetric stretching modes for the complexes with varied oxidational states. No splitting in Raman spectra for the pyridyl breathing line indicates similar bonding environment for both pyridyls in dpa^– , thus a delocalized structure in the [Ru₃]^6–8+ unit is proposed. For Ru₃(dpa)₄(CN)₂ complex series, we assign the infrared band at 302 cm^?1 to the Ru₃ asymmetric stretching mode and the weak Raman line at 285 cm^?1 to the Ru₃ symmetric stretching. Coordination to the strong axial ligand CN^– weakens the Ru‐Ru bonding. For the diruthenium nickel complex [Ru₂Ni(dpa)₄Cl₂]^0–1+, the diruthenium stretching mode ν_Ru‐Ru is assigned to the intense band at 327 and 333 cm^?1 in the Raman spectra for the neutral and oxidized forms, respectively. This implies a strong Ru‐Ru metal‐metal bonding.     

Reactivities governed by a single metal atom M in mixed-metal highnuclearity clusters having [Ru5M(C)] core (M = Co, Rh, Pd): Site-nonselective, site-selective, and chemo-selective variations in the SO2-trapping reactions

The SO₂ substitution for a CO ligand of the hexa-nuclear carbonyl complexes having Ru₅M(C) type carbido-metal core, [PPN][Ru₅Co(C)(CO)₁₆] (2), [PPN][Ru₅Rh(C)(CO)₁₆] (3), and Ru₅Pd(C)(CO)₁₆ (4), is dramatically affected by the kind of metal atom M: 2 (M = Co) is reactive but not site-selective, 3 (M = Rh) is reactive and site-selective, whereas 4 (M = Pd) is not reactive at all even though 4 can easily react with PPh₃ to give the substitution products.     

Quantum chemical study of the bond orders in the ruthenium,diruthenium and dirhodium nitrosyl complexes

Density functional calculations with the B3LYP functional were carried out for the [Ru(NO)Cl₅]²⁻, [Ru(NO)(NH₃)₅]³⁺, [Ru(NO)(CN)₅]²⁻, [Ru(NO)(CN)₅]³⁻, [Ru(NO)(hedta)]^q (hedta = N-(hydroxyethyl)ethylenediaminetriacetate triple-charged anion; q = 0, −1, −2), Rh₂(O₂CR)₄, Rh₂(O₂CR)₄(NO)₂, Ru₂(O₂CR)₄, Ru₂(O₂CR)₄(NO)₂, Ru₂(dpf)₄, and Ru₂(dpf)₄(NO)₂ (dpf = N,N′-diphenylformamidinate ion; R = H, CH₃, CF₃) complexes. The electronic structure was analyzed in terms of Mayer and Wiberg bond order indices. The technique of bond order indices decomposition into σ-, π-, and δ-contributions was proposed.     

Multiple one-electron oxidation and reduction of trinuclear bis(2,4-pentanedionato)ruthenium complexes with substituted diquinoxalino[2,3-a:2′,3′-c]phenazine ligands

The complexes (μ₃-L¹/L²)[Ru(acac)₂]₃, acac⁻ = 2,4-pentanedionato, L¹ = 2,3,8,9,14,15-hexachlorodiquinoxalino[2,3-a:2′,3′-c]phenazine and L² = 2,3,8,9,14,15- hexamethyldiquinoxalino[2,3-a:2′,3′-c]phenazine, undergo stepwise one-electron oxidation involving a total of three electrons and stepwise one-electron reduction with three (L²) or four electrons (L¹). All reversibly accessible states were characterized by UV–Vis–NIR spectroelectrochemistry. Oxidation leads to mixed-valent intermediates {(μ₃-L)[Ru(acac)₂]₃}⁺ and {(μ₃-L)[Ru(acac)₂]₃}²⁺ of which the Ru^IIIRu^IIRu^II combinations exhibit higher comproportionation constants K_c than the Ru^IIIRu^IIIRu^II states – in contrast to a previous report for the unsubstituted parent systems {(μ₃-L³)[Ru(acac)₂]₃}^+/2+, L³ = diquinoxalino[2,3-a:2′,3′-c]phenazine. No conspicuous inter-valence charge transfer absorptions were observed for the mixed-valent intermediates in the visible to near-infrared regions. The monocations and monoanions were characterized by EPR spectroscopy, revealing rhombic ruthenium(III) type signals for the former. Electron addition produces ruthenium(II) complexes of the reduced forms of the ligands L, a high resolution EPR spectrum with ¹⁴N and ^35,37Cl hyperfine coupling and negligible g anisotropy was found for {(μ₃-L¹)[Ru(acac)₂]₃}⁻. DFT calculations of (μ₃-L¹)[Ru(acac)₂]₃ confirm several ligand-centered low-lying unoccupied MOs for reduction and several metal-based high-lying occupied MOs for electron withdrawal, resulting in low-energy metal-to-ligand charge transfer (MLCT) transitions.     

Structural and mechanistic studies on ion insertion into the molecular box {[CpCo(CN)3]4[Cp*Ru]4}

The molecular box [CpCo(CN)₃]₄[Cp*Ru]₄ (Co₄Ru₄) reacts readily with a variety of monocations to form M⊂Co₄Ru₄⁺ (M=K⁺, Cs⁺, Rb⁺). Ion competition experiments, monitored by ESI-MS, show that the molecular box binds the smaller K⁺ more rapidly than Cs⁺, but that thermodynamically Co₄Ru₄ prefers the larger ion. The rates of ion-insertion for K⁺ and Cs⁺ into Co₄Ru₄ were found to qualitatively follow second order kinetics with K⁺, 300 M⁻¹ s⁻¹ and Cs⁺, 36 M⁻¹ s⁻¹. The ratio k_K/k_Cs qualitatively matched the ESI-MS results from ion competition experiments. The rates of ion-insertion into Co₄Ru₄ were found to depend on the counter anions. In particular, RbBF₄ reacted with Co₄Ru₄ more slowly than did RbOTf. The slower rates allowed us to establish second order kinetics. ¹H NMR studies reveal that the Cp signal for Co₄Ru₄ is very sensitive to the presence of entering ions, e.g., Rb⁺, whereas the corresponding Cp signal for Rb⊂Co₄Ru₄⁺ was insensitive to the presence of Rb⁺. The molecular structures of [Co₄Ru₄] · 6MeCN, [K⊂Co₄Ru₄]BF₄ · 7MeCN, [Cs⊂Co₄Ru₄]BF₄ · 6MeCN and [Tl⊂Co₄Ru₄]BF₄ · 6MeCN, determined by X-ray diffraction, showed that although the compounds crystallized in the same space group I23, a correlation exists between the Ru-N/Co-C bond distances and the size of the interstitial ion.     

Na27Ru14O48: A new mixed-valence sodium ruthenate with magnetic heptameric plaquettes

Na₂₇Ru₁₄O₄₈ has been synthesized in air at 700 °C. The composition and crystal structure of the phase were determined by single crystal X-ray diffraction. The triclinic crystal structure contains isolated planar Ru₇O₂₄ plaquettes made from seven edge-sharing RuO₆ octahedra. The complex Na:Ru ratio is a result of tilting of the plaquettes to disrupt the packing of nominally hexagonal close packed planes made of Na ions and RuO₆ octrahedra. Resistivity measurements show that the material is semiconducting with an activation energy of 0.53 eV. The observed magnetic moment of 3.11 μ_B per Ru is lower than the expected spin only value, but is within the range seen in other compounds and is too large to indicate that the fundamental magnetic entities are the isolated Ru₇O₂₄ plaquettes. Small, reproducible deviations in the Curie-Weiss behavior occur below 200 K and the onset of a broad magnetic transition is seen between 40 and 32 K.     

Ruthenium(III) mediated C-H activation of azonaphthol: Synthesis, structural characterization and transfer hydrogenation of ketones

Treatment of [RuCl₃(PPh₃)₃] with 1-(arylazo)naphthol ligands in benzene under reflux afford air-stable new organoruthenium(III) complexes with general composition [Ru(an-R)Cl(PPh₃)₂] (where, R = H, Cl, CH₃, OCH₃, OC₂H₅) in fairly good yield. The 1-(arylazo)naphtholate ligands behave as dianionic tridentate C, N, O donors and coordinates to ruthenium through phenolic oxygen, azo nitrogen and ortho carbon generate two five-membered chelate rings. The composition of the complexes have been established by analytical (elemental analysis and magnetic susceptibility measurement) and spectral (FT-IR, UV-Vis, EPR) methods. The complexes are paramagnetic (low-spin, d⁵) in nature and in dichloromethane solution show intense d-d transitions and ligand-to-metal charge transfer (LMCT) transitions in the visible region. The solution EPR spectrum of complex [Ru(an-CH₃)Cl(PPh₃)₂] (3) in dichloromethane at 77 K shows rhombic distortion around the ruthenium ion with three different ‘g’ values (g_x ≠ g_y ≠ g_z). The single crystal structure of the complex [Ru(an-OCH₃)Cl(PPh₃)₂] (4) has been characterised by X-ray crystallography, indicates the presence of a distorted octahedral geometry in these complexes. All the complexes exhibit one quasi-reversible oxidative response in the range 0.60-0.79 V (Ru^IV/Ru^III) and two quasi-reversible reductive responses (Ru^III/Ru^II; Ru^II/Ru^I) within the range −0.50 to −0.62 V and −0.93 to −0.98 V respectively. The formal potential of all the couples correlate linearly with the Hammett constant of the para substituent in arylazo fragment of the 1-(arylazo)naphtholate ligand. Further, the catalytic efficiency of one of the ruthenium complexes (4) was determined for the transfer hydrogenation of ketones with an excellent yield up to 99% in the presence of isopropanol/KOH.     

Magnetic single-component molecular conductors exhibiting strong π-d interactions

Single-component molecular conductors [M(tmdt)₂] (tmdt = trimethylenetetrathiafulvalenedithiolate; M = Ni, Au, Pt, Cu), exhibit a variety of electromagnetic properties, which originate from the differences of the metal’s d-orbitals role in the band structure formation. The [Au(tmdt)₂] crystal undergoes an antiferromagnetic transition at 110 K, while maintaining a metallic state at lower temperatures. The Au analog has a high magnetic transition temperature as compared to traditional magnetic molecular conductors due to the strong three-dimensional (3-D) structure and the contribution of the metal d-orbitals. The single-component molecular conductor, [Cu(tmdt)₂], with π- and d-like frontier orbitals is isostructural with other metallic [M(tmdt)₂] systems (M = Ni, Pt, Au). The Cu(tmdt)₂ molecule is planar, which strikingly contrasts the tetrahedral coordination of Cu(dmdt)₂ (dmdt = dimethyltetrathiafulvalenedithiolate) with similarly extended TTF type ligands. Interestingly, unlike other [M(tmdt)₂] with metallic behavior, [Cu(tmdt)₂] shows semiconducting behavior at room temperature (σ(RT) = ∼7 S cm⁻¹). The RT conductivity increased linearly with increased pressure to 110 S cm⁻¹ at 15 kbar despite the compressed pellet sample. The magnetic susceptibility indicates one-dimensional (1-D) Heisenberg behavior with J = 117 cm⁻¹ and shows antiferromagnetic ordering at 13 K. The [Cu(tmdt)₂] is a new multi-frontier π-d system, which introduces a d(σ)-type frontier orbital around the Fermi level of the π-like metal bands.     

Chemical bonding in EuTGe (T=Ni, Pd, Pt) and physical properties of EuPdGe

EuPdGe was prepared from the elements by reaction in a sealed tantalum tube in a high-frequency furnace. Magnetic susceptibility measurements show Curie-Weiss behavior above 60 K with an experimental magnetic moment of 8.0(1)μ_B/Eu indicating divalent europium. At low external fields antiferromagnetic ordering is observed at T_N=8.5(5) K. Magnetization measurements indicate a metamagnetic transition at a critical field of 1.5(2) T and a saturation magnetization of 6.4(1)μ_B/Eu at 5 K and 5.5 T. EuPdGe is a metallic conductor with a room-temperature value of 5000±500 μΩ cm for the specific resistivity. ¹⁵¹Eu Mössbauer spectroscopic experiments show a single europium site with an isomer shift of δ=−9.7(1) mm/s at 78 K. At 4.2 K full magnetic hyperfine field splitting with a hyperfine field of B=20.7(5) T is observed. Density functional calculations show the similarity of the electronic structures of EuPdGe and EuPtGe. T-Ge interactions (T=Pd, Pt) exist in both compounds. An ionic formula splitting Eu²⁺T⁰Ge²⁻ seems more appropriate than Eu²⁺T²⁺Ge⁴⁻ accounting for the bonding in both compounds. Geometry optimizations of EuTGe (T=Ni, Pt, Pd) show weak energy differences between the two structural types.     

Synthesis, spectroscopic and electrochemical studies of a series of transition metal complexes with amino- or bis(bromomethyl)-substituted dppz-ligands: Building blocks for fullerene-based donor-bridge-acceptor dyads

Transition metal complexes with ligands based on dipyrido[3,2-a:2′,3′-c]phenazine (dppz) have been synthesized. As metal fragments the [Ru(bpy)₂]⁺, Re(CO)₃Cl and the [Cu(PPh₃)₂]⁺ moieties have been used. The complexes containing amino- or bis(bromomethyl) substituted dppz ligands can be used for fullerene-based donor-bridge-acceptor dyads. The electronic absorption spectra of these complexes and of the dppz ligands were investigated. The dppz ligands show strong absorptions in the 300 and 390 nm region. An additional absorption band in the visible region (∼440 nm) is observed for the amino-substituted dppz-ligands. Ruthenium complexes exhibited broad absorption bands at 350-500 nm arising from intraligand-based transitions and the MLCT transition. MLCT transitions of the Re(I) and Cu(I) complexes are observed as shoulders of the stronger ligand-based absorption band tailing out to 400-500 nm. The electrochemically active complexes and ligands were studied by cyclic voltammetry and square-wave voltammetry. All ligands show one first reversible one-electron reduction located at the phenazine portion. These reductions are shifted to more positive redox potentials upon complexation. Oxidation potentials for reversible processes could be determined for the Ru²⁺/Ru³⁺ couple. For rhenium(I) and copper(I) complexes one irreversible oxidation process is observed.     

Ruthenium(II) carbonyl complexes of dehydroacetic acid thiosemicarbazone: Synthesis, structure, light emission and biological activity

The reaction of [RuHCl(CO)(B)(EPh₃)₂] (where E = As, B = AsPh₃; E = P, B = PPh₃, py, pip, or mor) and dehydroacetic acid thiosemicarbazone (abbreviated as H₂dhatsc where H₂ stands for the two dissociable protons) in benzene under reflux afford a series of new ruthenium(II) carbonyl complexes containing dehydroacetic acid thiosemicarbazone of general formula [Ru(dhatsc)(CO)(B)(EPh₃)] (where E = As, B = AsPh₃; E = P, B = PPh₃, py, pip or mor; dhatsc = dibasic tridentate dehydroacetic acid thiosemicarbazone). All the complexes have been characterized by elemental analyses, FT-IR, UV-Vis, and ¹H NMR spectral methods. The thiosemicarbazone of dehydroacetic acid behaves as dianionic tridentate O, N, S donor and coordinates to ruthenium via phenolic oxygen of dehydroacetic acid, the imine nitrogen of thiosemicarbazone and thiol sulfur. In chloroform solution, all the complexes exhibit metal-to-ligand charge transfer transitions (MLCT). The crystal structure of one of the complexes [Ru(dhatsc)(CO)(PPh₃)₂] (1) has been determined by single crystal X-ray diffraction which reveals the presence of a distorted octahedral geometry in the complexes. All the complexes exhibit an irreversible oxidation (Ru^III/Ru^II) in the range 0.76-0.89 V and an irreversible reduction (Ru^II/Ru^I) in the range −0.87 to −0.97 V. Further, the free ligand and its ruthenium complexes have been screened for their antibacterial and antifungal activities. The complexes show better activity in inhibiting the growth of bacteria Staphylococcus aureus and Escherichia coli and fungus Candida albicans and Aspergillus niger. These results made it desirable to delineate a comparison between free ligand and its ruthenium complexes.     

New diruthenium vinyliminium complexes from the insertion of alkynes into bridging aminocarbynes

Primary alkynes R′CCH [R′ = Me₃Si, Tol, CH₂OH, CO₂Me, (CH₂)₄CCH, Me] insert into the metal-carbon bond of diruthenium μ-aminocarbynes [Ru₂{μ-CN(Me)(R)}(μ-CO)(CO)(MeCN)(Cp)₂][SO₃CF₃] [R = 2,6-Me₂C₆H₃ (Xyl), 1a; CH₂Ph (Bz), 1b; Me, 1c] to give the vinyliminium complexes [Ru₂{μ-η¹:η³-C(R′)CHCN(Me)(R)}(μ-CO)(CO)(Cp)₂][SO₃CF₃] [R = Xyl, R′ = Me₃Si, 2a; R = Bz, R′ = Me₃Si, 2b; R = Me, R′ = Me₃Si, 2c; R = Xyl, R′ = Tol, 3a; R = Bz, R′ = Tol, 3b; R = Bz, R′ = CH₂OH, 4; R = Bz, R′ = CO₂Me, 5a; R = Me, R′ = CO₂Me, 5b; R = Xyl, R′ = (CH₂)₄CCH, 6; R = Xyl, R′ = Me, 7a; R = Bz, R′ = Me, 7b; R = Me, R′ = Me, 7c]. The related compound [Ru₂{μ-η¹:η³-C[C(Me)CH₂]CHCN(Me)(Xyl)}(μ-CO)(CO)(Cp)₂][SO₃CF₃], (9) is better prepared by reacting [Ru₂{μ-CN(Me)(Xyl)}(μ-CO)(CO)(Cl)(Cp)₂] (8) with AgSO₃CF₃ in the presence of HCCC(Me)CH₂ in CH₂Cl₂ at low temperature.In a similar way, also secondary alkynes can be inserted to give the new complexes [Ru₂{μ-η¹:η³-C(R′)C(R′)CN(Me)(R)}(μ-CO)(CO)(Cp)₂][SO₃CF₃] (R = Bz, R′ = CO₂Me, 11; R = Xyl, R′ = Et, 12a; R = Bz, R′ = Et, 12b; R = Xyl, R′ = Me, 13). The reactions of 2-7, 9, 11-13 with hydrides (i.e., NaBH₄, NaH) have been also studied, affording μ-vinylalkylidene complexes [Ru₂{μ-η¹:η³-C(R′)C(R″)C(H)N(Me)(R)}(μ-CO)(CO)(Cp)₂] (R = Bz, R′ = Me₃Si, R″ = H, 14a; R = Me, R′ = Me₃Si, R″ = H, 14b; R = Bz, R′ = Tol, R″ = H, 15; R = Bz, R′ = R″ = Et, 16), bis-alkylidene complexes [Ru₂{μ-η¹:η²-C(R′)C(H)(R″)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)₂] (R′ = Me₃Si, R″ = H, 17; R′ = R″ = Et, 18), acetylide compounds [Ru₂{μ-CN(Me)(R)}(μ-CO)(CO)(CCR′)(Cp)₂] (R = Xyl, R′ = Tol, 19; R = Bz, R′ = Me₃Si, 20; R = Xyl, R′ = Me, 21) or the tetranuclear species [Ru₂{μ-η¹:η²-C(Me)CCN(Me)(Bz)}(μ-CO)(CO)(Cp)₂]₂ (23) depending on the properties of the hydride and the substituents on the complex. Chromatography of 21 on alumina results in its conversion into [Ru₂{μ-η³:η¹-C[N(Me)(Xyl)]C(H)CCH₂}(μ-CO)(CO)(Cp)₂] (22). The crystal structures of 2a[CF₃SO₃] · 0.5CH₂Cl₂, 12a[CF₃SO₃] and 22 have been determined by X-ray diffraction studies.