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Four new Cu/PPh3/naphtoquinone complexes were synthesized, characterized (IR, UV/visible, 1D/2D NMR, mass spectrometry, elemental analysis, and X-ray diffraction), and evaluated as anticancer agents. We also investigated the reactive oxygen species (ROS) generation capacity of complex 4, considering the well-established photochemical property of naphthoquinones. Therefore, employing the electron paramagnetic resonance (EPR) "spin trap", 5,5-dimethyl-1-pyrroline N-oxide (DMPO) technique, we identified the formation of the characteristic •OOH species (hydroperoxyl radical) adduct even before irradiating the solution containing complex 4. As the irradiation progressed, this radical species gradually diminished, primarily giving rise to a novel species known as •DMPO-OH (DMPO + •OH radical). These findings strongly suggest that Cu(I)/PPh3/naphthoquinone complexes can generate ROS, even in the absence of irradiation, potentially intensifying their cytotoxic effect on tumor cells. Interpretation of the in vitro cytotoxicity data of the Cu(I) complexes considered their stability in cell culture medium. All of the complexes were cytotoxic to the lung (A549) and breast tumor cell lines (MDA-MB-231 and MCF-7). However, the higher toxicity for the lung (MRC5) and breast (MCF-10A) non-tumoral cells resulted in a low selectivity index. The morphological analysis of MDA-MB-231 cells treated with the complexes showed that they could cause decreased cell density, loss of cell morphology, and loss of cell adhesion, mainly with concentrations higher than the inhibitory concentration of 50% of cell viability (IC50) values. Similarly, the clonogenic survivance of these cells was affected only with concentrations higher than the IC50 values. An antimigratory effect was observed for complexes 1 and 4, showing around 20–40% of inhibition of wound closure in the wound healing experiments. [ABSTRACT FROM AUTHOR]

Copper nitrite reductase mimetics were synthesized using three new tridentate ligands sharing the same N,N,N motif of coordination. The ligands were based on L -proline modifications, attaching a pyridine and a triazole to the pyrrolidine ring, and differ by a pendant group (R = phenyl, n-butyl and n-propan-1-ol). All complexes coordinate nitrite, as evidenced by cyclic voltammetry, UV-Vis, FTIR and electron paramagnetic resonance (EPR) spectroscopies. The coordination mode of nitrite was assigned by FTIR and EPR as κ2O chelate mode. Upon acidification, EPR experiments indicated a shift from chelate to monodentate κO mode, and 15N NMR experiments of a Zn2+ analogue, suggested that the related Cu(II) nitrous acid complex may be reasonably stable in solution, but in equilibrium with free HONO under non catalytic conditions. Reduction of nitrite to NO was performed both chemically and electrocatalytically, observing the highest catalytic activities for the complex with n-propan-1-ol as pendant group. These results support the hypothesis that a hydrogen bond moiety in the secondary coordination sphere may aid the protonation step. [ABSTRACT FROM AUTHOR]

Herein we report the synthesis and characterization of a new copper(I) complex with triphenylphosphine (PPh3) and N‐(2‐thiophenecarbonyl)‐N'‐(3‐Cl, 4‐F‐phenyl)thiourea (HL), as ligands. The complex was characterized by vibrational (FTIR and FT‐Raman) and multinuclear (1H, 13C {1H}, 31P{1H}) NMR spectroscopies. The crystalline structure of the complex was determined by single‐crystal X‐ray diffraction, confirming that a neutral binuclear compound, identified as [Cu(PPh3)(L‐κ2‐N,μ‐S)]2, was obtained. The anionic thiourea ligand coordinates to the metal through the sulfur and nitrogen atoms in an unusual bidentate κ2‐N,μ‐S coordination mode. The complex is a dimer sited on a crystallographic center of symmetry. Each Cu2(μ‐S)2 cation bridges trough the sulfur atoms of two symmetry related thiourea moieties and is also coordinated to the nitrogen atom of the thiourea ligand and the phosphorus atom from PPh3 co‐ligand, forming a slightly distorted tetrahedral geometry. An intramolecular N−H⋅⋅⋅O=C hydrogen bond is observed in the anionic ligand, forming a six‐membered ring that stabilizes the N−H thioamide group. Hirshfeld surface analysis shows that the molecules are connected by weak intermolecular contacts C⋅⋅⋅C, H⋅⋅⋅C and H⋅⋅⋅H which add to the stability of the crystalline packing. The in vitro cytotoxicity study of the complex indicates that it is more active against human lung carcinoma cells (A549), when compared to the free ligand. [ABSTRACT FROM AUTHOR]

We have synthesized and characterized three new ruthenium(II) diphosphine complexes containing an acylthiourea ligand, with the general formula [Ru(DPEPhos)(O,S)(bipy)]PF6, where DPEPhos = bis(2-(diphenylphosphino)phenyl)ether, bipy = 2,2′-bipyridine, and O,S = N,N-dimethyl-N′-(benzoyl)thiourea (1), N,N-dimethyl-N′-(furoyl)thiourea (2), and N,N-dimethyl-N′-(thiophenyl)thiourea (3), by several physicochemical techniques. We evaluated the ruthenium complexes for their cytotoxicity against two human cancer cell lines, A549 (lung) and MDA-MB-231 (breast), and two corresponding lines of non-cancer cells, MRC-5 (lung) and MCF-10A (breast). All the complexes are cytotoxic against the cancer cell lines; the IC50 values lie in the micromolar range (0.07–0.70 μM). Ruthenium complex 1 is more selective (7 times more active) toward lung cancer cells (A549) than toward non-cancer cells (MRC-5) and is 160 times more cytotoxic than cisplatin against A549 cells. Investigations of the mechanism of action of complex 1 in A549 cells demonstrated that it inhibits colony formation and promotes cell cycle arrest in the G1 phase and apoptotic cell death. DNA binding studies revealed that complexes 1–3 interact with the biomolecule via minor grooves. These complexes also interact with human serum albumin (HSA) and have affinity for site I by hydrophobic forces. Therefore, this new class of ruthenium complexes can act as cytotoxic agents, mainly for lung cancer treatment. [ABSTRACT FROM AUTHOR]

Herein we discuss five ruthenium(II) complexes with good cytotoxicity against cancer cells. These complexes are named [Ru(tzdt)(bipy)(dppb)]PF6 (1), [Ru(mmi)(bipy)(dppb)]PF6 (2), [Ru(dmp)(bipy)(dppb)]PF6 (3), [Ru(mpca)(bipy)(dppb)]PF6 (4) and [Ru(2mq)(bipy)(dppb)]PF6 (5), where tzdt = 1,3-thiazolidine-2-thione, mmi = mercapto-1-methyl-imidazole, dmp = 4,6-diamino-2-mercaptopyrimidine, mpca = 6-mercaptopyridine-3-carboxylic acid, 2mq = 2-mercapto-4(3H)-quinazolinone, bipy = 2,2′-bipyridine and dppb = 1,4-bis(diphenylphosphino)butane. In vitro cell culture experiments revealed significant cytotoxic activity for 1–5 against MDA-MB-231, MCF-7, A549, DU-145 and HepG2 tumor cells, higher than that for the standard anticancer drug cisplatin. Compound/DNA interaction studies were carried out showing that 1–5 interact with DNA by electrostatic force of attraction or by hydrogen bonding. Moreover, the complexes interact, moderately and spontaneously, with human serum albumin (HSA) through the hydrophobic region. The five complexes are able to inhibit the DNA supercoiled relaxation mediated by human topoisomerase IB (TopIB), and complex 1 is found to be the most efficient TopIB inhibitor among the five compounds. The inhibitory effect and analysis of different steps of the TopIB catalytic cycle indicate that complex 1 inhibits the cleavage reaction impeding the binding of the enzyme to DNA and has no effect on the religation step. Complexes 1, 2 and 3 did not show mutagenic activity when they were evaluated by the cytokinesis-block micronucleus cytome assay in HepG2 cells and the Ames test in the presence and absence of mouse liver S9 metabolic activation. Therefore, it is necessary to perform further in-depth analysis of the therapeutic potential of these promising ruthenium complexes as anticancer drugs. [ABSTRACT FROM AUTHOR]

This manuscript describes the preparation of a new Ru(ii) nitrosylsulphito complex, trans-[Ru(NH3)4(isn)(N(O)SO3)]+ (complex 1), its spectroscopic and structural characterization, photochemistry, and thermal reactivity. Complex 1 was obtained by the reaction of sulfite ions (SO32−) with the nitrosyl complex trans-[Ru(NH3)4(isn)(NO)]3+ (complex 2) in aqueous solution resulting in the formation of the N-bonded nitrosylsulphito (N(O)SO3) ligand. To the best of our knowledge, only four nitrosylsulphito metal complexes have been described so far (J. Chem. Soc., Dalton Trans., 1983, 2465–2472), and there is no information about the photochemistry of such complexes. Complex 1 was characterized by spectroscopic means (UV-Vis, EPR, FT-IR, 1H- and 15N-NMR), elemental analysis and single-crystal X-ray diffraction. The X-ray structure of the precursor complex 2 is also discussed in the manuscript and is used as a reference for comparisons with the structure of 1. Complex 1 is water-soluble and kinetically stable at pH 7.4, with a first-order rate constant of 3.1 × 10−5 s−1 for isn labilization at 298 K (t1/2∼ 373 min). Under acidic conditions (1.0 M trifluoroacetic acid), 1 is stoichiometrically converted into the precursor complex 2. The reaction of hydroxide ions (OH−) with 1 and with 2 yields the Ru(ii) nitro complex trans-[Ru(NH3)4(isn)(NO2)]+ with second-order rate constants of 2.1 and 10.5 M−1 s−1 (at 288 K), respectively, showing the nucleophilic attack of OH− at the nitrosyl in 2 (Ru–NO) and at the nitrosylsulphito in 1 (Ru–N(O)SO3). The pKa value of the –SO3 moiety of the N(O)SO3 ligand in 1 was determined to be 5.08 ± 0.06 (at 298 K). The unprecedented photochemistry of a nitrosylsulphito complex is investigated in detail with 1. The proposed mechanism is based on experimental (UV-Vis, EPR, NMR and Transient Absorption Laser Flash Photolysis) and theoretical data (DFT) and involves photorelease of the N(O)SO3− ligand followed by formation of nitric oxide (NOṖ) and sulfite radicals (SO3Ṗ−, sulfur trioxide anion radical). [ABSTRACT FROM AUTHOR]

A novel mixed platinum(II) complex with general formula [Pt(PPh3)2(L1‐O,S)]PF6 has been synthetized and characterized by elemental analysis, molar conductivity, and by IR and NMR (1H, 13C and 31P) spectroscopic methods. The crystal structure has been determined by single‐crystal X‐ray crystallography. The molecule presents an almost ideal square‐planar geometry, and the crystal is stabilized by weak C–H···O and C–H···F hydrogen bonds, and C–H···π stacking interactions. The steric congestion of ligands is described by "exact" cone and solid cone angles, and the percentage of metal surface shielded by the ligands. The results are compared to closely related palladium complexes. The X‐ray structure revealed the proximity of the ortho phenyl proton of one PPh3 ligand to platinum(II) showing rare intramolecular C–H···Pt anagostic binding interaction. The title complex was determined to be active against tumor cells, and it also showed a moderate inhibitory action against mycobacterium tuberculosis. [ABSTRACT FROM AUTHOR]

We report the preparation, X-ray structure, chemical properties, and electron paramagnetic resonance (EPR) studies at Q and X-bands and temperature (mainly) T = 293 K of powder and oriented single crystal samples of the new compound [Cu(N′,N′-dimethyl-N′-benzoylthiourea)(2,2′-bipyridine)Cl], called CuBMB. The EPR spectra of single crystal samples at the Q-band display abrupt merging and narrowing of the peaks corresponding to two rotated copper sites as a function of magnetic field (B0) orientation. This behaviour indicates a quantum transition from an array of quasi-isolated spins to a quantum-entangled spin array associated with exchange narrowing processes and produced by weak intermolecular exchange interactions Ji between neighbour copper spins. This transition occurs when the magnitudes of the anisotropic contributions to the Zeeman couplings, tuned with the direction of B0, approach these ☋Ji☋ and produce level crossings. The exchange couplings between neighbour spins are estimated from the angular variation of the single crystal EPR results at the Q-band. We analyse the quantum behaviour and phase transitions of the spin system and discuss the magnitudes of the exchange couplings in terms of the structure of the chemical paths connecting Cu neighbours. The single crystal data at the Q-band indicates an uncommon ground electronic state of CuII which is discussed and compared with the results of DFT calculations. The spectrum of polycrystalline (powder) samples at the Q-band is a sum of contributions of microcrystals in each phase, and the fraction F of the entangled phase depends on the microwave frequency. The X-band spectrum is compatible with the Q-band results, but does not display a transition, and the spin system is in the quantum-entangled phase for all field orientations. This behaviour is further studied with a simple geometric model giving basic predictions. The crystal structure of CuBMB is monoclinic, space group P21/n, with a = 11.9790(3) Å, b = 14.0236(5) Å, c = 12.1193(3) Å, β = 104.952(2)° and Z = 4, and the copper ions are equatorially bonded to the benzoylthiourea and bipyridine ligands in a heavily distorted square pyramidal structure. [ABSTRACT FROM AUTHOR]

Organometallic ruthenium complexes as potential anticancer agents have been explored due to their suitable properties, such as stability in the solid state and in solution, water solubility and low toxicity. In this study, eight metal complexes of this class were synthesized, characterized and their important biological activities against a human breast tumor cell line (MDA-MB-231) were studied. Complexes 1–8 were obtained in good yields and have been characterized by satisfactory elemental analyses, IR, 1D and 2D 1H and 13C{1H} NMR, UV-Vis spectroscopy, cyclic voltammetry, ESI-MS and X-ray diffractometry (1, 2, 3 and 6). All complexes exhibit growth inhibition on human breast and lung tumor cell lines, with IC50 values ranging from 6.0 to 45.0 μM in 48 h. Four compounds were selected to evaluate the changes in the morphology, clonogenic, migration, cell cycle arrest and cell death in MDA-MB-231 cells. The complexes are able to induce morphological changes and inhibit the size, number of colonies and cell migration, and induce cell cycle arrest in the sub-G1 phase and apoptosis cell death. The interaction of the complexes with DNA was determined by performing spectroscopic titration, a competitive assay with thiazole orange, circular dichroism, gel electrophoresis and interactions with guanosine or guanosine monophosphate by 1H NMR, indicating the non-covalent interaction. The HSA binding affinity measured by spectrophotometric titration, revealed the hydrophobic and spontaneous association with the human protein. Overall, the studies indicated that these metal complexes are potential agents against MDA-MB-231 cells, encouraging us to continue studies of these types of compounds. [ABSTRACT FROM AUTHOR]

Three iso-structural Zn(II), Cd(II), and Hg(II) complexes with 1-benzyl-2-phenyl-1H-benzimidazole (BPB), ZnBPB, CdBPB, and HgBPB, respectively, were synthesized by reaction of the ligand with the corresponding metal chlorides in methanolic solutions. The complexes [MCl2(BPB)2], where M?=?Zn(II), Cd(II), or Hg(II), were characterized by elemental analysis,13C,1H, and [1H–15N] heteronuclear multiple bond coherence NMR measurements, and Raman spectroscopy. The structures of the cadmium and mercury complexes were solved by single-crystal X-ray diffraction, while the structure of the zinc complex was determined by X-ray powder diffraction. The three compounds crystallize in the triclinic system inP-1space group with the metal ions lying in a distorted tetrahedral environment. The zinc complex shows high luminescence in the solid state at room temperature. [ABSTRACT FROM AUTHOR]

Salicylaldehyde 2-chlorobenzoyl hydrazone (H2LASSBio-466), salicylaldehyde 4-chlorobenzoyl hydrazone (H2LASSBio-1064) and their complexes [Zn(LASSBio-466)H2O]2 (1) and [Zn(HLASSBio-1064)Cl]2 (2) were evaluated in animal models of peripheral and central nociception, and acute inflammation. All studied compounds significantly inhibited acetic acid-induced writhing response. Upon coordination the antinociceptive activity was favored in the complex 1. H2LASSBio-466 inhibited only the first phase of the formalin test, while 1 was active in the second phase, like indomethacin, indicating its ability to inhibit nociception associated with the inflammatory response. Hence coordination to zinc(II) altered the pharmacological profile of H2LASSBio-466. H2LASSBio-1064 inhibited both phases but this effect was not improved by coordination. The studied compounds did not increase the latency of response in the hot plate model, indicating their lack of central anti-nociceptive activity. All compounds showed levels of inhibition of zymosan-induced peritonitis comparable or superior to indomethacin, indicating an expressive anti-inflammatory profile. [ABSTRACT FROM AUTHOR]

Three new homodinuclear complexes containing substituted phenolate-type ligands based on the N5O2 donor (2-(N,N-Bis(2-pyridylmethyl)aminomethyl)-6-(N′,N′-(2-hydroxybenzyl)(2-pyridylmethyl))aminomethyl)-4-methylphenol (H2L-H) were synthesized and characterized by X-ray crystallography. Potentiometric titration studies in 70% (v/v) aqueous ethanol show that all three complexes exhibit a common {CuII(µ-phenoxo)(µ-OH)CuII(OH)} core in solution. Kinetic studies on the oxidation reaction of 3,5-di-tert-butylcatechol revealed that the catalytic activity of the metal complexes increases toward the ligand containing an electron-donating group. In addition, these complexes also carried out DNA cleavage by hydrolytic and oxidative pathways. Copyright © 2010 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Synthesis, characterization, crystal structure, and biological studies of two complexes with glycolic acid are described. The solid complexes were formulated as K2[VO(C2H2O3)(C2H3O3)2] · H2O (1) and K2[{VO2(C2H2O3)}2] (2) and characterized by X-ray studies, Fourier transform infrared spectroscopy (FTIR), Electron paramagnetic resonance (EPR), and magnetic susceptibility. Conversion of 1 to 2 was studied in aqueous solution by UV-Vis spectroscopy and in the solid state by diffuse reflectance spectroscopy. Complex 2 contains dinuclear [{VO2(C2H2O3)}2]2- anions in which glycolate(2-) is a five-membered chelating ring formed by carboxylate and α-hydroxy groups. The geometry around the vanadium in 2 was interpreted as intermediate between a trigonal bipyramid and a square pyramid. Vanadium(IV) is pentacoordinate in 1 as a distorted square pyramid. Complex 1 contains a vanadyl group (V=O) surrounded by two oxygens from deprotonated carboxylate and hydroxy groups forming a five-membered ring. Two oxygens from different glycolates(1-) are bonded to the (V=O) also. Biological analysis for potential cytotoxic effects of 1 was performed using Human Cervix Adenocarcinoma (HeLa) cells, a human cervix adenocarcinoma-derived cell line. After incubation for 48 h, 1 causes 90 and 95% of HeLa cells death at 20 and 200 μmol L-1, respectively. [ABSTRACT FROM AUTHOR]

α-diamines, such as ethylendiamine and o-phenylendiamine, add to 3,4-aryl-disubstituted 1,2,5-thiadiazole 1,1-dioxides to give dihydropyrazines or quinoxalines, respectively and sulfamide. The new compound acenaphtho [5,6-b]-2,3-dihydropyrazine was synthesized and characterized. The addition of ethylendiamine to 3,4-diphenyl- 1,2,5-thiadiazoline 1,1-dioxide gives 3,4-disubstituted thiadiazolidine 1,1-dioxide, dihydropyrazines, or pyrazines, depending on the reaction condition used. The reactions were followed by cyclic voltammetry and NMR spectroscopy which, in some cases, allowed the detection of the thiadiazolidine intermediate. Copyright © 2008 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

In a search for new antitumoral agents, a series of homoleptic copper(II) complexes with amino acids and dipeptides, as well as heteroleptic complexes containing both dipeptides and 1,10-phenanthroline, were studied. Furthermore, a single-crystal structure containing alanyl-leucinato ([Cu3(AlaLeu)3(H2O)3(CO3)]·PF6·H2O), which is the first homotrinuclear carbonato-bridged copper(II) complex with a dipeptide moiety, is presented. To assess possible antitumor action mechanisms, we focused on the comparative analysis of pro- and antioxidant behaviors. Pro-oxidant activity, in which the reactive oxygen species (ROS) formed by the reaction of the complexes with H2O2 produce oxidative damage to 2-deoxy-d-ribose, was evaluated using the TBARS method. Additionally, the antioxidant action was quantified through the superoxide dismutase (SOD)-like activity, using a protocol based on the inhibitory effect of SOD on the reduction of nitrobluetetrazolium (NBT) by the superoxide anion generated by the xanthine/xanthine oxidase system. Our findings show that Cu–amino acid complexes are strong ROS producers and moderate SOD mimics. Conversely, Cu–dipeptide–phen complexes are good SOD mimics but poor ROS producers. The activity of Cu–dipeptide complexes was strongly dependent on the dipeptide. A DFT computational analysis revealed that complexes with high SOD-like activity tend to display a large dipole moment and condensed-to-copper charge, softness and LUMO contribution. Moreover, good ROS producers have higher global hardness and copper electrophilicity, lower copper softness and flexible and freely accessible coordination polyhedra. [ABSTRACT FROM AUTHOR]

A series of cis-{RuCl2(PPh3)2[4,4′-(X)2-2,2′-bipy]} [ cis-chlorines; X=-H, -Me, -SMe, and (-Cl,-Me)] complexes have had their structures determined by single crystal X-ray diffraction. The geometry of these complexes, also determined in CH2Cl2 solution by 31P{1H}-n.m.r. spectroscopy, showed that the chemical shifts for the phosphorus atoms are slightly dependent on the p Ka of the 4,4′-(-X)2-2,2′-bipy ligands. [ABSTRACT FROM AUTHOR]

In this work a series of {[RuCl 2 (dppb)](μ-4,4′-N-N)} 4 complexes were synthesized and characterized by elemental analysis, cyclic voltammetry and differential pulse voltammetry and UV-Vis and 31 P{ 1 H} NMR spectroscopies; [(μ-4,4′-N-N=pyrazine (pz), 4,4′-bipyridine=(4,4′-bipy), 1,2-bis- trans -(4-pyridyl)ethane = (pyeta) and 1,2-bis- trans -(4-pyridyl)ethylene=(pyetil) as bridging alterdentate ligands (alterdentate ligands are molecules (or ions), with two equivalent ligating atoms or ligating sites that do not simultaneously bind to a metallic center [Zelewsky von A. in Stereochemistry of Coordination Compounds , Inorganic Chemistry , A Textbook Series; John Wiley & Sons, Inc.: New York, 1995: p. 45] [1] ) and 1,4-bis(diphenylphosphino)butane=dppb]. Electrochemical experiments (cyclic voltammetry and differential pulse voltammetry) suggest that for longer ligands the interaction between two ruthenium atoms is weak and for short ligands like pyrazine the corresponding interaction is strong. The analysis of the X-ray structure of the {[RuCl 2 (dppb)](μ-4,4′-bipy)} 4 complex showed that the molecular squares obtained are stacked on top of each other along the α axis forming infinite columns and that the formation of central tunnels is prevented by the bulky character of the phenyl groups of the diphenylphosphine ligands. [ABSTRACT FROM AUTHOR]

The crystal structure of the complexes [Zn(sac)2(im)2] (1) and [Zn(sac)2(bzim)2]2·.2EtOH·H2O (2) (sac = saccharinate anion; im = imidazole; bzim = benzimidazole; EtOH = ethanol) was determined by single crystal X-ray diffractometry. Complex 1 crystallizes in the monoclinic P21/n space group with a = 9.1585(5), b = 16.4409(6), c = 15.0249(5) Å, β = 94.079(1)°, and Z = 4, whereas complex 2 belongs to the triclinic space group P 1 with a = 10.8500(2), b = 12.4860(2), c = 13.5640(3) Å, α = 115,696(1), β = 100.086(1), γ = 102.169(l)°, and Z = 1. In both complexes, the Zn(II) cations are in a slightly distorted tetrahedral ZnN4 environment, coordinated to two saccharinate anions and to two imidazole (1) and to two benzimidazole (2) molecules. The complexes were also characterized by means of infrared spectroscopy and their thermal behavior investigated by means of thermogravimetric and differential thermal analytical techniques. [ABSTRACT FROM AUTHOR]

The reaction of lapachol, 2-hydroxy-3-(3-methyl-2-butenyl)-1,4-naphtoquinone, C 15 H 14 O 3 , with zinc acetate, in ethanol, produces a chelate formula Zn(C 15 H 13 O 3 ) 2 (C 2 H 6 O) 2 , whose structure has been determined by single crystal X-ray diffraction. It pertains to the triclinic system, space group P (No. 2), a = 8.2380(3) Å, b = 9.4900(2) Å, c = 11.0110(4) Å, α = 112.536(2)°, β = 91.204(2)°, γ = 92.664(2)°, Z = 1. Some spectroscopic and chemical properties of the complex are also reported. [ABSTRACT FROM AUTHOR]

The crystal structure of the title complex, [Cd( tsac)2(H2O)], has been determined by single crystal X-ray diffraction methods. It crystallizes in the monoclinic space group C2/c ( a = 12.236(3), b = 8.919(3), c = 16.655(3) Å, β = 96.18(2)°, Z = 4). The molecular structure was solved from 1705 independent reflections with I > σ( I) and refined to R1 = 0.0489. Infrared and Raman spectra of the complex were recorded and are briefly discussed. Its thermal behaviour was investigated by thermogravimetry and differential thermal analysis. [ABSTRACT FROM AUTHOR]

The ruthenium(II) complex, [RuCl[sub 2] (NO)L] (I), (L = [(2-py)[sub 2] PC[sub 2] H[sub 4] PO[sub 2] (2-py)][sup -] ) was obtained from recrystallization of RuCl[sub 3] NO(d2pype) (d2pype = (2-py)[sub 2] PC[sub 2] H[sub 4] P(2-py)[sub 2] ) in the presence of HNO[sub 3] , crystallizing in the monoclinic space group P2[sub 1 ] (no. 4), with a = 8.012(4) Å, b = 14.454(4) Å, c = 9.353(3) Å, β = 105.77(3)°, and Z = 2. Crystals of the DMSO solvate of the complex (II) were obtained from (CD[sub 3] )[sub 2] SO solution, crystallizing in the monoclinic space group P2[sub 1] /c (no.14) with a = 9.7080(2) Å, b = 22.2920(5) Å, c = 11.5230(3) Å, β = 92.0450(10)°, and Z = 4. In both complexes, the geometry about the ruthenium atom is a distorted octahedron mainly as a result of the tridentate [P,N,O]-bonding mode of L. The ν (NO) bands at 1875 cm[sup –1] in both complexes are consistent with the linear disposition of the NO group and the Ru atom as is observed in the X-ray crystal structure (Ru-N1-O1 angle = 178.5(4)°).Key words: pyridylphosphine, nitrosyl, ruthenium complex, X-ray structure.La recristallisation du RuCl[sub 3] NO(d2pype) (d2pype = (2-(py)[sub 2] PC[sub 2] H[sub 4] P(2-py)[sub 2] ) en présence de HNO[sub 3] conduit à la formation du complexe de ruthénium(II), [RuCl[sub 2] (NO)L] (1), (L = [(2-py)[sub 2] PC[sub 2] H[sub 4] P(2py)[sub 2] )][sup -] ) qui cristallise dans le groupe d'espace P2[sub 1] (no. 4), avec a = 8,012(4) Å, b = 14,454(4) Å et c = 9,353(3) Å, β = 105,77(3)° et Z = 2. Les cristaux du produit de solvatation du complexe par le DMSO (2) ont été obtenus à partir d'une solution de (CD[sub 3] )[sub 2] SO; ils cristallisent dans le groupe d'espace P2[sub 1] /c (no.14) avec a = 9,7080(2) Å, b = 22,2920(5) Å et c = 11,5230(3) Å, β = 92,0450(10)° et Z = 4. Dans les deux complexes, la géométrie autour de l'atome de ruthénium est un octaèdre déformé en raison principalement du mode de liaison tridentate [P,N,O] de L. Les fréquences des bandes NO, à 1875 cm[sup –1] , dans les deux complexes sont en accord avec une disposition linéaire du groupe NO et de l'atome de Ru; c'est ce qui est observé dans la structure cristalline obtenue par diffraction des rayons X alors que l'angle Ru-N1-O1 est de 178,5(4)°.Mots clés : pyridylphosphine, nitrosyle, complexe du ruthénium, structure cristalline par diffraction des rayons X.[Traduit par la Rédaction] [ABSTRACT FROM AUTHOR]

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Presents the synthesis of two cages derived from 1,2,4-triphosphol. Formation of isomers; Purification by chromatography.

The crystal structure of the title compound, [Hg(C11H8N)(C12H22PS2)], consists of mol­ecules in which the Hg atom is coordinated strongly to the C atom in position 2 of the phenyl group and to one of the di­thio­phosphinate S atoms, and at longer distances to the pyridine N atom and the other S atom. The C-Hg-S fragment involving the S atom more strongly bound to Hg is almost linear [C-Hg-S = 178.9 (3)°]. [ABSTRACT FROM AUTHOR]