Nickel(II) Coordination Polymers Supported by Bis-pyridyl-bis-amide and Angular Dicarboxylate Ligands: Role of Ligand Flexibility in Iodine Adsorption

Reactions of N‚N’-bis(3-pyridylmethyl)oxalamide (L¹), N‚N’-bis(4-pyridylmethyl)oxalamide (L²), or N,N’-bis(3-pyridylmethyl)adipoamide) (L³) with angular dicarboxylic acids and Ni(II) salts under hydro(solvo)thermal conditions afforded a series of coordination polymers: {[Ni(L¹)(OBA)(H₂O)]·H₂O}_n (H₂OBA = 4,4-oxydibenzoic acid), 1, {[Ni(L¹)(SDA)(H₂O)₂]·H₂O·CH₃OH}_n (H₂SDA = 4,4-sulfonyldibenzoic acid), 2, {[Ni(L²)(OBA)]·C₂H₅OH}_n, 3, {[Ni(L²)(OBA)]·CH₃OH}_n, 4, {[Ni₂(L²)(SDA)₂(H₂O)₃]·5H₂O}_n, 5, {[Ni₂(L²)(SDA)₂(H₂O)₃]·H₂O·2C₂H₅OH}_n, 6, {[Ni(L³)(OBA)(H₂O)₂]·2H₂O}_n, 7, {[Ni(L³)(SDA)(H₂O)₂]·2H₂O}_n, 8, and {[Ni(L³)₀.₅(SDA)(H₂O)₂]·0.5C₂H₅OH}_n, 9, which have been structurally characterized by using single-crystal X-ray crystallography. Complex 1 exhibits an interdigitated 2D layer with the 2,4L2 topology and 2 is a 2D layer with the sql topology, while 3 and 4 are 3D frameworks resulting from polycatenated 2D nets with the sql topology and 5 and 6 are 2-fold interpenetrated 3D frameworks with the dia topology. Complexes 7 and 8 are 1D looped chains and 9 is a 2D layer with the 3,4L13 topology. The various structural types in 1–9 indicate that the structural diversity is subject to the flexibility and donor atom position of the neutral spacer ligands and the identity of the angular dicarboxylate ligands, while the role of the solvent is uncertain. The iodine adsorption of 1–9 was also investigated, demonstrating that that the flexibility of the spacer L¹–L³ ligands can be an important factor that governs the feasibility of the iodine adsorption. Moreover, complex 9 shows a better iodine adsorption and encapsulates 166.55 mg g⁻¹ iodine in the vapor phase at 60 °C, which corresponded to 0.38 molecules of iodine per formula unit.     

Supramolecular Coordination Polymers by Self-assembling of Bis-monodentate Ligands with HgI2

Two supramolecular coordination polymers, [HgI₂(L¹)·0.5H₂O]_∞ (1) and [HgI₂(L²)·0.4CH₃OH]_∞ (2), have been prepared by ligands L¹ (L¹ = bis[4-(4- pyridylmethyleneamino)phenyl] ether) and L² (L² = N,N′-bis(3-pyridylmethyl)-diphthalic diimide) with HgI₂, respectively. 1 formed an interestingly infinite cross-linked double helical structure, whereas 2 formed the one-dimensional zigzag chains, which are parallel with each other.     

In Vitro Activity of Copper(II) Complexes,Loaded or Unloaded into a Nanostructured Lipid System,against Mycobacterium tuberculosis

Tuberculosis (TB) is an infectious disease caused mainly by the bacillus Mycobacterium tuberculosis (Mtb), presenting 9.5 million new cases and 1.5 million deaths in 2014. The aim of this study was to evaluate a nanostructured lipid system (NLS) composed of 10% phase oil (cholesterol), 10% surfactant (soy phosphatidylcholine, sodium oleate), and Eumulgin^® HRE 40 ([castor oil polyoxyl-40-hydrogenated] in a proportion of 3:6:8), and an 80% aqueous phase (phosphate buffer pH = 7.4) as a tactic to enhance the in vitro anti-Mtb activity of the copper(II) complexes [CuCl₂(INH)₂]·H₂O (1), [Cu(NCS)₂(INH)₂]·5H₂O (2) and [Cu(NCO)₂(INH)₂]·4H₂O (3). The Cu(II) complex-loaded NLS displayed sizes ranging from 169.5 ± 0.7095 to 211.1 ± 0.8963 nm, polydispersity index (PDI) varying from 0.135 ± 0.0130 to 0.236 ± 0.00100, and zeta potential ranging from −0.00690 ± 0.0896 to −8.43 ± 1.63 mV. Rheological analysis showed that the formulations behave as non-Newtonian fluids of the pseudoplastic and viscoelastic type. Antimycobacterial activities of the free complexes and NLS-loaded complexes against Mtb H₃₇Rv ATCC 27294 were evaluated by the REMA methodology, and the selectivity index (SI) was calculated using the cytotoxicity index (IC₅₀) against Vero (ATCC^® CCL-81), J774A.1 (ATCC^® TIB-67), and MRC-5 (ATCC^® CCL-171) cell lines. The data suggest that the incorporation of the complexes into NLS improved the inhibitory action against Mtb by 52-, 27-, and 4.7-fold and the SI values by 173-, 43-, and 7-fold for the compounds 1, 2 and 3, respectively. The incorporation of the complexes 1, 2 and 3 into the NLS also resulted in a significant decrease of toxicity towards an alternative model (Artemia salina L.). These findings suggest that the NLS may be considered as a platform for incorporation of metallic complexes aimed at the treatment of TB.     

Formation of an unusual copper(II) complex from the degradation of a novel tricopper(II) carbohydrazone complex

An unusual copper(II) complex [Cu(L^1a)₂Cl₂] CH₃OH·H₂O·H₃O⁺Cl⁻ (1a) was isolated from a solution of a novel tricopper(II) complex [Cu₃(HL¹)Cl₂]Cl₃·2H₂O (1) in methanol, where L^1a is 3-(2-pyridyl)triazolo[1,5-a]-pyridine, and characterized with single crystal X-ray diffraction study. The tricopper(II) complex of potential ligand 1,5-bis(di-2-pyridyl ketone) carbohydrazone (H₂L¹) was synthesized and physico-chemically characterized, while the formation of the complex 1a was followed by time-dependant monitoring of the UV–visible spectra, which reveals degradation of ligand backbone as intensity loss of bands corresponding to O → Cu(II) charge transfer.     

Evaluation of the In Vitro and In Vivo Efficacy of Ruthenium Polypyridyl Compounds against Breast Cancer

The clinical success of cisplatin, carboplatin, and oxaliplatin has sparked the interest of medicinal inorganic chemistry to synthesize and study compounds with non-platinum metal centers. Despite Ru(II)–polypyridyl complexes being widely studied and well established for their antitumor properties, there are not enough in vivo studies to establish the potentiality of this type of compound. Therefore, we report to the best of our knowledge the first in vivo study of Ru(II)–polypyridyl complexes against breast cancer with promising results. In order to conduct our study, we used MCF7 zebrafish xenografts and ruthenium complexes [Ru(bipy)₂(C₁₂H₈N₆-N,N)][CF₃SO₃]₂ Ru1 and [{Ru(bipy)₂}₂(μ-C₁₂H₈N₆-N,N)][CF₃SO₃]₄ Ru2, which were recently developed by our group. Ru1 and Ru2 reduced the tumor size by an average of 30% without causing significant signs of lethality when administered at low doses of 1.25 mg·L⁻¹. Moreover, the in vitro selectivity results were confirmed in vivo against MCF7 breast cancer cells. Surprisingly, this work suggests that both the mono- and the dinuclear Ru(II)–polypyridyl compounds have in vivo potential against breast cancer, since there were no significant differences between both treatments, highlighting Ru1 and Ru2 as promising chemotherapy agents in breast cancer therapy.     

Ruthenium(III) Complexes of Heterocyclic Tridentate (ONN) Schiff Base: Synthesis,Characterization and its Biological Properties as an Antiradical and Antiproliferative Agent

The current work reports the synthesis, spectroscopic studies, antiradical and antiproliferative properties of four ruthenium(III) complexes of heterocyclic tridentate Schiff base bearing a simple 2′,4′-dihydroxyacetophenone functionality and ethylenediamine as the bridging ligand with RCHO moiety. The reaction of the tridentate ligands with RuCl₃·3H₂O lead to the formation of neutral complexes of the type [Ru(L)Cl₂(H₂O)] (where L = tridentate NNO ligands). The compounds were characterized by elemental analysis, UV-vis, conductivity measurements, FTIR spectroscopy and confirmed the proposed octahedral geometry around the Ru ion. The Ru(III) compounds showed antiradical potentials against 2,2-Diphenyl-1-Picrylhydrazyl (DPPH) and 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radicals, with DPPH scavenging capability in the order: [(PAEBOD)RuCl₂] > [(BZEBOD)RuCl₂] > [(MOABOD)RuCl₂] > [Vit. C] > [rutin] > [(METBOD)RuCl₂], and ABTS radical in the order: [(PAEBOD)RuCl₂] < [(MOABOD)RuCl₂] < [(BZEBOD)RuCl₂] < [(METBOD)RuCl₂]. Furthermore, in vitro anti-proliferative activity was investigated against three human cancer cell lines: renal cancer cell (TK-10), melanoma cancer cell (UACC-62) and breast cancer cell (MCF-7) by SRB assay.     

Metallkomplexe mit biologisch wichtigen Liganden. CXXIII. Darstellung von Isophthaloyl‐ und Terephthaloyl‐di‐[(β,γ,δ)‐amino‐α‐aminocarboxylat]‐verbrückten zweikernigen Ruthenium‐, Rhodium‐ und Iridium‐Halbsandwich‐Komplexen

The reaction of the Cu(II) bis N,O‐chelate‐complexes of L‐2,4‐diaminobutyric acid, L‐ornithine and L‐lysine {Cu[H₂N–CH(COO)(CH₂)_nNH₃]₂}²⁺(Cl^–)₂ (n = 2–4) with terephthaloyl dichloride or isophthaloyl dichloride gives the polymeric complexes {‐OC–C₆H₄–CO–NH–(CH₂)_n–CH(nh₂)(COO)Cu(OOC)(NH₂)CH–CH₂)_n–NH‐}_x 1 – 5 . From these the metal can be removed by precipitation of Cu(II) with H₂S. The liberated ω,ω′‐N,N′‐diterephthaloyl (or iso‐phthaloyl)‐diaminoacids 6 – 10 react with [Ru(cymene)Cl₂]₂, [Ru(C₆Me₆)Cl₂]₂, [Cp*RhCl₂]₂ or [Cp*IrCl₂]₂ to the ligand bridged bis‐amino acidate complexes [L_n(Cl)M–(OOC)(NH₂)CH–(CH₂)_nNH–CO]₂–C₆H₄ 11 – 14 .     

Diruthenium(I,I) Catalysts for the Formation of β‐ and γ‐Lactams via Carbenoid C?H Insertion of α‐Diazoacetamides

Intramolecular carbenoid C H insertion of five α‐diazoacetamides [N₂CH CONR₂, NR₂=NEt₂ ( 3a ), NBu₂ ( 3b ), N(i‐Pr)₂ ( 3c ), N(CH₂Ph)₂ ( 3d ), N(i‐Pr)(CH₂Ph) ( 3e )], was investigated using as catalysts dinuclear Ru(I,I) complexes of the type [Ru₂(μ‐L¹)₂(CO)₄L²₂], where L¹ is a bidentate bridging acetate, calix[4]arenedicarboxylate, saccharinate, pyridin‐2‐olate, or triazenide ligand, as well as [RuCl₂(p‐cymene)]₂. The Ru(I,I) complexes were found to be suitable catalysts for the carbenoid cyclization reactions, except in the case of 3a . With diazoamides 3b–e , [Ru₂(μ‐sac)₂(CO)₅]₂ (sac=saccharinate) and [Ru₂(μ‐6‐chloropyridin‐2‐olate)₂(CH₃CN)₂(CO)₄] are as effective as Rh₂(OAc)₄ under the same conditions, although some differences in the regioselectivity and chemoselectivity of the cyclization are observed. The carbenoid cyclization reactions yield γ‐lactams from diazoamides 3a and 3b , both a β‐ and a γ‐lactam from 3c , and a β‐lactam as well as a 3‐azabicyclo[5.3.0]deca‐5,7,9‐trien‐2‐one from 3d . With 3e , formation of γ‐lactam 21 and of bicyclic lactam 23 prevails.     

Crystal Engineering Based on Polymeric Hydrogen-Bonded Supramolecules by Self-Assembling of 9, 10-Bis(3,5-dihydroxyphenyl)anthracene and 2,2′,4,4′-Tetrahydroxybenzophenone with Bipyridines

9, 10-bis(3,5-dihydroxyphenyl)anthracene (BDHA) and 2,2′,4,4′-tetrahydroxybenzophenone (THB) are crystallized with bipyridine bases 4,4′-bipyridyl (bipy), 1,2-bis(4-pyridyl)ethane (bipy-eta), 1,2-di(4-pyridyl)ethylene (dipy-ete), 1,3-di(4-pyridyl)propane (dipy-pra), 4,4′-dipyridyl sulfide (dipy-sul), and 4,4′-dipyridyl disulfide (dipy-dis) to afford molecular complexes (BDHA)·(bipy)₂1, (BDHA) · (bipy-eta)₂2, (BDHA)_0.5· (dipy-pra) ·CH₃CH₂OH 3, (BDHA)_0.5· (dipy-sul) ·H₂O 4, (BDHA)_0.5· (dipy-dis) ·CH₃CH₂OH 5 and (THB) · (dipy-ete)₂·H₂O 6. The crystal structures of 1–6 have been determined by single-crystal X-ray diffraction. All these molecular complexes exhibit polymeric supramolecular structures via O–H· · ·N or O–H· · ·O hydrogen-bonding. 1 and 2 form infinitely rectangular macrocycles linked with one another, whose sizes are ca.12.477 å × 4.802 å and ca.14.575 å × 4.809 å, respectively. 3, 5 and 6 form the one-dimensional zigzag chain structure. 4 forms a ladder structure, and two dipy-sul molecules were included in a frame.     

8-Hydroxyquinoline-Amino Acid Hybrids and Their Half-Sandwich Rh and Ru Complexes: Synthesis,Anticancer Activities,Solution Chemistry and Interaction with Biomolecules

Solution chemical properties of two novel 8-hydroxyquinoline-D-proline and homo-proline hybrids were investigated along with their complex formation with [Rh(η⁵-C₅Me₅)(H₂O)₃]²⁺ and [Ru(η⁶-p-cymene)(H₂O)₃]²⁺ ions by pH-potentiometry, UV-visible spectrophotometry and ¹H NMR spectroscopy. Due to the zwitterionic structure of the ligands, they possess excellent water solubility as well as their complexes. The complexes exhibit high solution stability in a wide pH range; no significant dissociation occurs at physiological pH. The hybrids and their Rh(η⁵-C₅Me₅) complexes displayed enhanced cytotoxicity in human colon adenocarcinoma cell lines and exhibited multidrug resistance selectivity. In addition, the Rh(η⁵-C₅Me₅) complexes showed increased selectivity to the chemosensitive cancer cells over the normal cells; meanwhile, the Ru(η⁶-p-cymene) complexes were inactive, most likely due to arene loss. Interaction of the complexes with human serum albumin (HSA) and calf-thymus DNA (ct-DNA) was investigated by capillary electrophoresis, fluorometry and circular dichroism. The complexes are able to bind strongly to HSA and ct-DNA, but DNA cleavage was not observed. Changing the five-membered proline ring to the six-membered homoproline resulted in increased lipophilicity and cytotoxicity of the Rh(η⁵-C₅Me₅) complexes while changing the configuration (L vs. D) rather has an impact on HSA or ct-DNA binding.     

Unsaturated Copolyesters from Macrolactone/Norbornene: Toward Reaction Kinetics of Metathesis Copolymerization Using Ruthenium Carbene Catalysts

Unsaturated copolyesters are of great interest in polymer science due to their broad potential applications and sustainability. Copolyesters were synthesized from the ring-opening metathesis copolymerization of ω-6-hexadecenlactone (HDL) and norbornene (NB) using ruthenium-alkylidene [Ru(Cl₂)(=CHPh)(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(PCy₃)] (Ru1), [Ru(Cl)₂(=CHPh)(PCy₃)₂] (Ru2), and ruthenium-vinylidene [RuCl₂(=C=CH(p-C₆H₄CF₃))(PCy₃)₂] (Ru3) catalysts, respectively, yielding HDL-NB copolymers with different ratios of the monomer HDL in the feed. The activity of N-heterocyclic-carbene (NHC) (Ru1) and phosphine (Ru2 and Ru3) ligands containing ruthenium-carbene catalysts were evaluated in the synthesis of copolymer HDL-NB. The catalysts Ru1 with an NHC ligand showed superior activity and stability over catalysts Ru2 and Ru3 bearing PCy₃ ligands. The incorporation of the monomers in the copolymers determined by ¹H-NMR spectroscopy was similar to that of the HDL-NB values in the feed. Experiments, at distinct monomer molar ratios, were carried out using the catalysts Ru1–Ru3 to determine the copolymerization reactivity constants by applying the Mayo–Lewis and Fineman–Ross methods. The copolymer distribution under equilibrium conditions was studied by the ¹³C NMR spectra, indicating that the copolymer HDL-NB is a gradient copolymer. The main factor determining the decrease in melting temperature is the inclusion of norbornene units, indicating that the PNB units permeate trough the HDL chains. The copolymers with different molar ratios [HDL]/[NB] have good thermal stability up to 411 °C in comparison with the homopolymer PHDL (384 °C). Further, the stress–strain measurements in tension for these copolymers depicted the appreciable increment in stress values as the NB content increases.     

Cu(II) bipyridine and phenantroline complexes: Tailor-made catalysts for the selective oxidation of tetralin

Mononuclear Cu(II) complexes have been synthesized, and their structure thoroughly characterized by electrospray ionization mass spectrometry (ESI-MS). These 2,2′-bipyridine and 1,10-phenantroline mononuclear Cu(II) complexes have been tested as catalysts in the partial oxidation of tetralin (1,2,3,4-tetrahydronaphthalene), using hydrogen peroxide as oxidant in acetonitrile/water as solvent.The complexes [Cu(bipy)₃]Cl₂·6H₂O (1), [Cu(bipy)₂Cl]Cl·5H₂O (2), [Cu(bipy)Cl₂] (3), [Cu(phen)₃]Cl₂·6H₂O (4), [Cu(phen)₂Cl]Cl·5H₂O (5), [Cu(phen)Cl₂] (6) were able to oxidize tetralin at room temperature, at high degrees of conversion (62.1% with 2) into α-tetralol and α-tetralon at 91% selectivity (81% in 1-tetralon).Depending on nature and number of ligands (bipyridine or phenantroline) surrounding Cu²⁺ cation, one was able to tailor both the activity toward tetralin oxidation, and the selectivity toward 1-tetralol and 1-tetralone products, but also to raise the yield in valuable α-tetralone.     

Photoinduced linkage isomerism of binuclear bis(pyrazole-3,5-dicarboxylato)-bridged {RuNO} centres

The two novel binuclear pyrazole-3,5-dicarboxylato-bridged {RuNO}⁶ complexes K₂[{Ru(NO)Cl}₂(μ-pzdc)₂] (1) and [{Ru(NO)(H₂O)}₂(μ-pzdc)₂]·4H₂O (2) (pzdc = pyrazole-3,5-dicarboxylate) were synthesized and characterized by elemental analysis, mass spectrometry and spectroscopic methods (NMR, UV–vis, IR). 2 was investigated by means of single-crystal X-ray diffraction analysis. On irradiation, in both 1 and 2 the existence of photoinduced long-lived metastable isonitrosyl states SI were detected by low-temperature infrared spectroscopy.     

Polymeric structures of a pair of linear,dicarboxylate (tpy)2Ru2+ analogues

The preparation and solid-state structures of homoleptic Ru(II) complexes based on the ligands 4′-(4-carboxyphenyl)tpy (L₁) (where tpy = 2,2′:6′,2″-terpyridine) and 4′-(4-carboxyphenyl)-4,4″-di-(tert-butyl)tpy (L₂) are described. Both complexes are found to possess polymeric solid-state structures due to hydrogen-bonding interactions. The first complex, [Ru(L₁)₂]²⁺, exhibits a more closely-packed structure relative to that of [Ru(L₂)₂]²⁺, which was found to have a porous solid-state structure due to the steric bulk of the tert-butyl groups.     

Catalytic properties of Ru-η-C6H6-diphosphine complexes for hydrogenation of benzene in aqueous-organic biphasic system

The influences of pH on the catalytic properties of Ru-η⁶-C₆H₆-diphosphine complex [RuCl(η⁶-C₆H₆)(BISBI)]Cl (1) (BISBI = 2,2′-bis(diphenylphosphinomethyl)-1,1′-biphenyl), [RuCl(η⁶-C₆H₆)(BDPX)]Cl (2) (BDPX = 1,2-bis(diphenylphosphinomethyl)benzene), Ru₂Cl₄(η⁶-C₆H₆)₂(μ₂-BDNA) (3) (BDNA = 1,8-bis(diphenylphosphinomethyl)naphthalene), [RuCl(η⁶-C₆H₆)(BISBI)]BF₄ (4), [RuCl(η⁶-C₆H₆)(BDPX)]BF₄ (5), and [(η⁶-C₆H₆)₂Ru₂Cl₂(μ₂-Cl)(μ₂-BDNA)]BF₄ (6) for the hydrogenation of benzene were investigated in aqueous-organic biphasic system. The hydrogenation of benzene catalyzed by all complexes yielded only cyclohexane. The catalytic results revealed that the stabilities of these complexes were not only closely relative with their compositions or molecular structures but also the pH value of aqueous solution. Complexes 1 and 2 were homogeneous catalysts at pH <5, but complexes 3, 4, 5 and 6 were partly decomposed in the same reaction conditions and played simultaneously the roles of homogeneous and heterogeneous catalysts. When the pH was up to 12, all of six complexes were gradually decomposed to Ru(0) particles. The addition of extra phosphine ligand was favorable to prevent these complexes from decomposing in the catalytic process. The experiment of mercury poisoning and the curve of conversion vs time strongly supported above conclusions.     

Co-polymerization of propylene oxide and CO2 using early transition metal (groups IV and V) metallocalix[n]arenes (n = 4, 6, 8)

A number of metallocalix[n]arenes, where n = 4, 6, or 8, of titanium and vanadium have been screened for their ability to act as catalysts for the co-polymerization of propylene oxide and CO₂ to form cyclic/polycarbonates. The vanadium-containing catalysts, namely [VO(L¹Me)] (1), [(VO₂)L²H₆] (2), [Na(NCMe)₆]₂[(Na[VO]₄L²)(Na(NCMe))₃]₂ (3), [VO(μ-OH)L^3/H₂]₂∙6CH₂Cl₂ (4), {[VO]₂(μ-O)L⁴[Na(NCMe)₂]₂} (5), {[V(Np-tolyl)]₂L⁴} (6) and [V(Np-RC₆H₄)Cl₃] (R = Cl (7), OMe (8), CF₃ (9)), where L¹H₃ = methylether-p-tert-butylcalix[4]areneH₃, L²H₈ = p-tert-butylcalix[8]areneH₈, L³H₄ = p-tert-butylthiacalix[4]areneH₄, L⁴H₆ = p-tert-butyltetrahomodioxacalix[6]areneH₆, performed poorly, affording, in the majority of cases, TONs less than 1 at 90°C over 6 h and low molecular weight oligomeric products (M_n ≤ 1665). In the case of the titanocalix[8]arenes, {(TiX)₂[TiX(NCMe)]₂(μ₃-O)₂(L²)} (X = Cl (10), Br (11), I (12)), which all adopt a similar, ladder-type structure, the activity under the same conditions is somewhat higher (TONs >6) and follows the trend Cl > Br > I; by comparison the non-calixarene species [TiCl₄(THF)₂] was virtually inactive. In the case of 10, it was observed that the use of PPNCl (bis[triphenylphosphine]iminium chloride) as co-catalyst significantly improved both the polymer yield and molecular weight (M_n 3515). The molecular structures of the complexes [HNEt₃]₂[VO(μ-O)L³H₂]₂∙3CH₂Cl₂ (4∙3CH₂Cl₂), [VO(μ-OH)L^3/H₂]₂∙6CH₂Cl₂ (4^/) (where L^3/H₂ is a partially oxidized form of L³H₄) and {(TiCl)₂[TiCl(NCMe)]₂(μ₃-O)₂(L²)}·6.5MeCN (10·6.5MeCN) are reported.     

Reactions of benzene based half sandwich ruthenium(II) complex with 2,6-bis((phenylseleno)methyl)pyridine: Preferential substitution of ring resulting in a catalyst of high activity for oxidation of alcohols

[2,6-Bis((phenylseleno)methyl)pyridine] (L) a (Se, N, Se) pincer ligand synthesized by reacting PhSe^? (in situ generated) with 2,6-bis(chloromethyl)pyridine reacts with [{(η⁶-C₆H₆)RuCl(μ-Cl)}₂] (2:1 molar ratio) by preferential substitution of ring resulting in the first Ru-(Se, N, Se) pincer ligand complex, mer-[Ru(CH₃CN)₂Cl(L)][PF₆](1).H₂O. Similar reaction in 4:1 molar ratio results in mer-[Ru(L)₂][ClO₄]₂(2). The ¹H, ¹³C{¹H} and ⁷⁷Se{¹H} NMR spectra of L, 1 and 2 were found characteristic. The single crystal structures of 1 and 2 were studied by X-ray crystallography. The geometry of Ru in both the complexes is distorted octahedral. The Ru–Se distances are in the ranges 2.4412(16)–2.4522(16) and 2.4583(14)–2.4707(15) ? respectively for 1 and 2. The structural solutions from the crystal data in case of 2, due to inferior quality of its crystals, are suitable for supporting bonding mode of L with Ru(II) only. The 1 shows high catalytic activity for oxidation of primary and secondary alcohols (TON up to 9.7 × 10⁴).     

Homonuclear tris-dithiocarbamato ruthenium(III) complexes as single-molecule precursors for the synthesis of ruthenium(III) sulfide nanoparticles

Tris(N-phenyldithiocarbamato) ruthenium(III) complexes, [Ru(L¹)₃] (1); tris(N-(4-methylphenyl)dithiocarbamato)) ruthenium(III), [Ru(L²)₃] (2); and tris(N-(4-methoxyphenyl)dithiocarbamato)) ruthenium(III), [Ru(L³)₃] (3) were synthesized and characterized by elemental analysis, thermogravimetric analysis, FTIR, UV–VIS and NMR spectroscopy. TGA analyses show major degradation of all complexes in the range 120–350°C, leading to the formation of residual weight corresponding to ruthenium (III) sulfides. The ¹H-NMR spectra of the ligands and complexes are in agreement with the proposed structures. FTIR studies confirmed that the ligands coordinate the Ru³⁺ ion in a bidentate chelating mode. The complexes were thermolysed at 180°C to prepare hexadecylamine-capped Ru₂S₃ nanoparticles. Powder X-ray diffraction patterns revealed the formation of hexagonal-phase Ru₂S₃ nanoparticles with average crystallite sizes ranging from 8.3 to 9.5?nm. TEM images showed the crystalline clusters with shapes ranging from square to hexagonal, while SEM images elucidated that the particles were agglomerated. Energy-dispersive X-ray spectra confirmed the presents of Ru₂S₃ nanoparticles.     

Synthesis and characterization of trans-[Ru(NO)Cl(L)4](PF6)2 (L = isonicotinamide; 4-acetylpyridine) and related species

The trans-[RuCl₂(L)₄], trans-[Ru(NO)Cl (L)₄](PF₆)₂ (L = isonicotinamide and 4-acetylpyridine) and trans-[Ru(NO)(OH)(py)₄]Cl₂ (py = pyridine) complexes have been prepared and characterized by elemental analysis, UV–visible, infrared, and ¹H NMR spectroscopies, and cyclic voltammetry. The MLCT band energies of trans-[RuCl₂(L)₄] increase in the order 4-acpy < isn < py. The reduction potentials of trans-[RuCl₂(L)₄] and trans-[Ru(NO)Cl(L)₄]²⁺ increase in the order py < isn < 4-acpy. The stretching band frequency, ν_NO, of the nitrosyl complexes ranges from 1913 to 1852 cm^?1 indicating a nitrosonium character for the NO ligand. Due to the large π-acceptor ability of the equatorial ligands, the coordinated water is much more acidic in the water soluble trans-[Ru(NO)(H₂O)(py)₄]³⁺ than in trans-[Ru(NO)(H₂O)(NH₃)₄]³⁺.     

Homoleptic complexes [Ru(L-L)3]2+ (L-L=diphosphine,diarsine)

Homoleptic Ru(II)–diphosphine and Ru(II)–diarsine complexes [Ru(L-L)₃](OTf)₂ (L-L=Me₂P(CH₂)_nPMe₂; n=1, dmpm; n=2, dmpe) and 1,2-C₆H₄(AsMe₂)₂ (diars) have been isolated, in which the Ru(II) state is stabilised to an unprecedented degree, and the crystal structure of [Ru(diars)₃]Cl₂ has been determined.