Synthesis and properties of trinuclear polypyridyl complexes Ru(II)-Co(II)-Ru(II) and Ru(II)-Co(III)-Ru(II): Their photoinduced interconversion

The trinuclear [{Ru^II(bpy)₂(bpy-terpy)}₂Co^II]⁶⁺ complex (1⁶⁺) in which a Co(II)-bis-terpyridine-like centre is covalently linked to two Ru(II)-tris-bipyridine-like moieties by a bridging bipyridine-terpyridine ligand has been synthesised and characterised. Its electrochemical, photophysical and photochemical properties have been investigated in CH₃CN. The cyclic voltammetry exhibits two successive reversible oxidation processes, corresponding to the Co^III/Co^II and Ru^III/Ru^II redox couples at E_1/2 = −0.06 and 0.91 V vs Ag/Ag⁺ 10 mM, respectively. The one-electron oxidized form of the complex, [{Ru^II(bpy)₂(bpy-terpy)}₂Co^III]⁷⁺ (1⁷⁺) obtained after exhaustive electrolysis carried out at 0.2 V is fully stable. 1⁶⁺ and 1⁷⁺ are only poorly luminescent, indicating that the covalent linkage of the Ru(II)-tris-bipyridine centre to the cobalt subunit leads to a strong quenching of the Ru^II excited state by an intramolecular process. Luminescence lifetime experiments carried out at different temperatures indicate that the transfer is more efficient for 1⁷⁺ compare to 1⁶⁺ due to lower activation energy. Continuous irradiation of 1⁷⁺ performed at 405 nm in the presence of P(Ph)₃ acting as sacrificial electron donor leads to its quantitative reduction into 1⁶⁺, whereas similar experiment starting from 1⁶⁺ with a sulfonium salt as sacrificial electron acceptor converts 1⁶⁺ into 1⁷⁺ with a slower rate and a maximum yield of 80%. These photoinduced electron transfers were followed by UV-Visible spectroscopy and compared with those obtained with a simple mixture of both mononuclear parent complexes i.e. [Ru^II(bpy)₃]²⁺ and [Co^II(tolyl-terpy)₂]²⁺ or [Co^III(tolyl-terpy)₂]³⁺ (tolyl-terpy = 4′-(4-methylphenyl)-2,2′:6′,2′′-terpyridine).     

Zn(II)-113Cd(II) and Zn(II)-Mg(II) hybrids of alkaline phosphatase. 31P and 113Cd NMR

Methods have been developed for the addition of different metal ion species to the three distinct pairs of metal sites (A, B, and C) found in the dimer of apoalkaline phosphatase. This allows the preparation of hybrid alkaline phosphatases in which A and B sites of each monomer contain two different species of metal ion or the A and B sites of one monomer contain the same species of metal ion, while the adjacent monomer contains a second species. The following hybrids have been characterized in detail: (Zn(II)ACd(II)B)2 alkaline phosphatase, (Zn(II)AMg(II)B)2 alkaline phosphatase, (Cd(II)AZn(II)B)2 alkaline phosphatase, and (Zn(II)AZn(II]B)(Cd(II)ACd(II)B) alkaline phosphatase. 31P and, where appropriate, 113Cd NMR have been used to monitor the behavior of the covalent (E-P) and noncovalent (E X P) phosphointermediates and of the A and B metal ions. From the pH dependencies of the E-P in equilibrium E X P in equilibrium E + Pi equilibria, it is clear that A site metal is the dominant influence in dephosphorylation of E-P and may have a coordinated water molecule, which ionizes to ZnOH- at a low pH providing the nucleophile for dephosphorylation. A site metal also serves to coordinate phosphate in the E X P complex. B site metal has a much smaller effect on dephosphorylation rates, although it does dramatically alter the Pi dissociation rate, which is the rate-limiting step for the native enzyme at alkaline pH, and is probably important in neutralizing the charge on the phosphoseryl residue, thus potentiating the nucleophilic attack of the OH- bound at A site. Phosphate dissociation is slowed markedly by replacement of B site zinc by cadmium. There is clear evidence for long range effects of subunit-subunit interactions, since metal ion and phosphate binding at one active center alters the environments of A and B site metal ions and phosphoserine at the other active site.     

Nickel(II) and copper(II) complexes of mixed benzene-triazolehemiporphyrazines

The kinetics of substitution reactions of [η-CpFe(CO)₃]PF₆ with PPh₃ in the presence of R-PyOs have been studied. For all the R-PyOs (R = 4-OMe, 4-Me, 3,4-(CH)₄, 4-Ph, 3-Me, 2,3-(CH)₄, 2,6-Me₂, 2-Me), the reactions yeild the same product [η⁵-CpFe(CO)₂PPh₃]PF₆, according to a second-order rate law that is first order in concentrations of [η⁵-CpFe(CO)₃]PF₆ and of R-PyO but zero order in PPh₃ concentration. These results, along with the dependence of the reaction rate on the nature of R-PyO, are consistent with an associative mechanism. Activation parameters further support the bimmolecular nature of the reactions: ΔH^≠ = 13.4 ± 0.4 kcal mol⁻¹, ΔS^≠ = −19.1 ± 1.3 cal k⁻¹ mol⁻¹ for 4-PhPyO; ΔH^≠ = 12.3 ± 0.3 kcal mol⁻¹, ΔS^≠ = 24.7 ±1.0 cal K⁻¹ mol⁻¹ for 2-MePyO. For the various substituted pyridine N-oxides studied in this paper, the rates of reaction increase with the increasing electron-donating abilities of the substituents on the pyridine ring or N-oxide basicities, but decrease with increasing ¹⁷O chemical shifts of the N-oxides. Electronic and steric factors contributing to the reactivity of pyridine N-oxides have been quantitatively assessed.     

Chitosan-cobalt(II) and nickel(II) chelates as antibacterial agents

Antibacterial behavior of chitosan-bivalent metal chelates (Co and Ni) was investigated in vitro against standard bacteria, Staphylococcus aureus ATCC 4533, S. faecalis ATCC 8043 and Escherichia coli ATCC 25923. The chitosan-metal chelates were prepared by varying the molar ratio of metal ions to a fixed amount of chitosan. The metal ion contents, structural properties and morphology of the chelates were respectively determined using ICP-OES, FT-IR and SEM. All the chitosan-metal chelates showed wide spectrum of effective antibacterial activities better than free chitosan and the individual metal ions. The results indicated that inhibitory effects of the chelates were dependent not only on the property of the coordinated metal ion, but also on the molar ratio of the metal ion. Consequently, the ideal inhibitory effects could be obtained with metal ion of high charge intensity and when the molar ratio of chitosan to metal was above 1:1. These chelates are promising materials for novel antibacterial agents.     

Palladium(II) and platinum(II) complexes with polypyridylbenzene ligands

The ligands 1,3-bis(3-pyridyl)benzene (1), 1,3-bis(4-pyridyl)benzene (2) and 1,3,5-tris(4-pyridyl)benzene (3) have been prepared by Stille coupling of 3- or 4-trimethylstannylpyridine with the appropriate bromoarene. Ligands 1 and 2 react with [M(OTf)₂(dppp)] (M=Pd, Pt) to produce the dipalladium- or diplatinum-containing macrocycles [M₂(μ-1)₂(dppp)₂](OTf)₄ or [M₂(μ-2)₂(dppp)₂](OTf)₄. These have been characterized by NMR spectroscopy and mass spectrometry and, in the case of [Pd₂(μ-1)₂(dppp)₂](OTf)₄, by X-ray crystallography. The molecular structure of the [Pd₂(μ-1)₂(dppp)₂]⁴⁺ cation reveals a shallow arrangement of the aromatic rings, with the palladium atoms lying above and below. The tridentate ligand 3 reacts with [Pd(OTf)₂(dppp)] to produce a trimetallic species of the form [Pd₃(μ₃-3)₂(dppp)₃](OTf)₆.     

真菌吸附铅锌的研究

正随着采矿业的迅速发展,越来越多的重金属通过多种途径进入土壤环境中,对生态环境造成了不可估量的破坏并严重威胁人类健康。铅锌在工业上具有非常重要的作用且其应用极为广泛,而他们具有的难去除、难迁移和生物累积等特性使得铅锌在环境中的污染尤为突出。通过微生物的生长代谢,有效降低土壤重金属毒性,是促进植物生长的重要步骤之一。同时也要求微生物自身具有抵抗重金属的功能,根际微生     

Metal-ion environment in solid Mn(II), Co(II) and Ni(II) hyaluronates

Amorphous powders and films of some metal hyaluronate complexes of general composition (C14H20O11N)2 x xH2O (M = Mn2+, Ni2+ and Co2+) have been prepared at pH 5.5-6.0. The coordination geometry around the metal ions has been analyzed by EXAFS (extended X-ray absorption fine structure) and FTIR spectroscopy. Mn2+, Ni2+, and Co2+ ions are coordinated to carboxylate oxygen atoms and water molecules. The process of local geometry formation round the metal ions is sensitive to sample preparation.     

Equilibrium and structural studies on Co(II), Ni(II), Cu(II) and Zn(II) complexes with N-(2-benzimidazolyl)methyliminodiacetic acid: crystal structures of Ni(II) and Cu(II) complexes

Combined pH-metric, UV-Vis, ¹H NMR and EPR spectral investigations on the complex formation of M(II) ions (M=Co, Ni, Cu and Zn) with N-(2-benzimidazolyl)methyliminodiacetic acid (H₂bzimida, hereafter H₂L) in aqueous solution at a fixed ionic strength, I=10⁻¹ mol dm⁻³, at 25 ± 1 °C indicate the formation of M(L), M(H₋₁L)⁻ and M₂(H₋₁L)⁺ complexes. Proton-ligand and metal-ligand constants and the complex formation equilibria have been elucidated. Solid complexes, [M(L)(H₂O)₂] · nH₂O (n=1 for M = Co and Zn, n=2 for M = Ni) and {Cu (μ-L) · 4H₂O}_n, have been isolated and characterized by elemental analysis, spectral, conductance and magnetic measurements and thermal studies. Structures of [Ni(L)(H₂O)₂] · 2H₂O and {Cu(μ-L) · 4H₂O}_n have been determined by single crystal X-ray diffraction. The nickel(II) complex exists in a distorted octahedral environment in which the metal ion is coordinated by the two carboxylate O atoms, the amino-N atom of the iminodiacetate moiety and the pyridine type N-atom of the benzimidazole moiety. Two aqua O atoms function as fifth and sixth donor atoms. The copper(II) complex is made up of interpenetrating polymeric chains of antiferromagnetically coupled Cu(II) ions linked by carboxylato bridges in syn-anti (apical-equatorial) bonding mode and stabilized via interchain hydrogen bonds and π-π stacking interactions.     

The interaction of methylcobalamin with tetracyanoplatinate(II), tetrathiocyanoplatinate(II) and tetrachloroplatinate(II)

The interactions of methylcobalamin (CH₃-B₁₂) with Pt(CN)₄^2?, PtCl₄^2?, and Pt(SCN)₄^2? in aqueous solution were studied by UV-visible and ¹H NMR spectroscopy. Together with earlier results on the mechanism of the Pt(IV)-dependent methyl-transfer reaction from CH₃-B₁₂ to Pt(II), these studies suggest at least three Pt binding sites on CH₃-B₁₂. One site, which is occupied by all three complexes (K₁ = 4 X 10³ M^?1 for Pt(CN)₄^2? and 3 X 10³ M^?1 for PtCl₄^2?), is located on the CoCH₃ side of the corrin macrocycle, and is involved in the methyl-transfer process in the presence of a Pt(IV) complex. An additional site for Pt(SCN)₄^2? is the N-3 of the benzimidazole group, resulting in dissociation of this group from the cobalt. An additional site for Pt(CN)₄^2? has a binding constant of 16 M^1? and ¹H NMR changes indicate perturbation but not dissociation of the benzimidazole group. Only the first interaction is discerned for PtCl₄^2?.     

Triphenylbismuth seven-coordinate complexes of molybdenum(II) and tungsten(II)

The seven-coordinate complexes [MI₂(CO)₃(NCMe)₂] (M = Mo and W) react with one equivalent of BiPh₃ in CH₂Cl₂ at room temperature to give the monoacetonitrile complexes [MI₂(CO)₃(NCMe)(BiPh₃)]. The molybdenum complex [MoI₂(CO)₃(NCMe)(BiPh₃)] after stirring in CH₂Cl₂ at room temperature for 5 h affords the iodide-bridged dimer [Mo(μ-I)I(CO)₃(BiPh₃)]₂, whereas the tungsten complex [WI₂(CO)₃(NCMe)(BiPh₃)] does not appear to dimerise even after stirring for 48 h in CH₂Cl₂ at room temperature. Reaction of [MI₂(CO)₃(NCMe)₂] with two equivalents of BiPh₃ gives the bistriphenylbismuth compounds [MI₂(CO)₃(BiPh₃)₂] in good yield. The new mixed ligand complexes [MI₂(CO)₃L(BiPh₃)] were prepared either by reaction of [MI₂(CO)₃(NCMe)(BiPh₃)]in situ with one equivalent of L(L = P(OPh)₃), or an in situ reaction of [MI₂(CO)₃(NCMe)L] (L = PPh₃ and SbPh₃; and L = AsPh₃ and PPh₂Cy (for M = Mo only) with an equimolar quantity of BiPh₃. Reaction of [MoI₂(CO)₃(NCMe)(BiPh₃)] with one equivalent of 2,2′-bipyridyl (bipy) in CH₂Cl₂ at room temperature afforded the cationic complexes [MoI(CO)₃(bipy)(BiPh₃)]I in good yield. The complex [WI₂(CO)₃(NCMe)(BiPh₃)] (prepared in situ) reacts with two equivalents of NaS₂CNMe₂·2H₂O to eventually give the non-triphenylbismuth containing product [W(CO)₃(S₂CNMe₂)₂] in high yield.     

Biosorption of lead(II), cadmium(II), copper(II) and nickel(II) by anaerobic granular biomass

Biosorption is potentially an attractive technology for treatment of wastewater for retaining heavy metals from dilute solutions. This study investigated the feasibility of anaerobic granules as a novel type of biosorbent, for lead, copper, cadmium, and nickel removal from aqueous solutions. Anaerobic sludge supplied from a wastewater treatment plant in the province of Quebec was used. Anaerobic granules are microbial aggregates with a strong, compact and porous structure and excellent settling ability. After treatment of the biomass with Ca ions, the cation exchange capacity of the biomass was approximately 111 meq/100 g of biomass dry weight which is comparable to the metal binding capacities of commercial ion exchange resins. This work investigated the equilibrium, batch dynamics for the biosorption process. Binding capacity experiments using viable biomass revealed a higher value than those for nonviable biomass. Binding capacity experiments using non-viable biomass treated with Ca revealed a high value of metals uptake. The solution initial pH value affected metal sorption. Over the pH range of 4.0-5.5, pH-related effects were not significant. Meanwhile, at lower pH values the uptake capacity decreased. Time dependency experiments for the metal ions uptake showed that adsorption equilibrium was reached almost 30 min after metal addition. It was found that the q(max) for Pb2+, Cd2+, Cu2+, and Ni2+ ions, were 255, 60, 55, and 26 mg/g respectively (1.23, 0.53, 0.87, and 0.44 mmol/g respectively). The data pertaining to the sorption dependence upon metal ion concentration could be fitted to a Langmiur isotherm model. Based on the results, the anaerobic granules treated with Ca appear to be a promising biosorbent for removal of heavy metals from wastewater due to its optimal uptake of heavy metals, its particulate shape, compact porous structure, excellent settling ability, and its high mechanical strength.     

N-(2-Pyridyl)acetamide complexes of palladium(II), cobalt(II), nickel(II), and copper(II)

N-(2-Pyridyl)acetamide (aapH) complexes of palladium(II), cobalt(II), nickel(II), and copper(II) have been studied by means of magnetic susceptibilities, and infrared, electronic, and PMR spectra. In the octahedral complexes M(aapH)₂X₂(M = Co, Ni, Cu; X = Cl, Br, NCS, NO₃), bidentate aapH is chelated through the pyridine-N and amid-O atomes, whereas in the square-planar Pd(aapH)₂X₂ (X = Cl, Br) unidentate aapH is coordinated through the pyridine-N atom alone. Under alkaline conditions aapH is deprotonated in the presence of palladium(II) to form Pd(aap)₂·4H₂O, aap being an anionic bidentate ligand and chelating through the pyridine-N and amide-O atoms.     

Copper(II), cobalt(II) and nickel(II) complexes of alkyl-substituted tris(2-benzimidazolylmethyl)amines and their ternary copper(II) systems containing several thiolates

Copper(II), cobalt and nickel(II) complexes of tris(benzimidazolylmethyl)amine(1) and of its methyl(2), isobutyl(3) or isopropyl(4)-substituted derivatives of one of the backbone methylene groups were prepared and characterized. The ligands (1)–(3) afforded trigonal bipyramidal copper(II) complexes, whereas ligand (4) gave a tetrahedrally distorted tetragonal one because of the steric hindrance arising from the isopropyl group. All the cobalt(II) complexes prepared were supposed to be tetrahedral or pseudotrigonal bipyramidal, and all the nickel(II) complexes to be slightly tetrahedrally distorted octahedral. Ternary copper(II) systems containing several thiolates as the third component exhibited intense blue, brown or green color under a reduced temperature by virtue of the charge transfer bands, S^? → Cu.     

Ditopic bis(oxazolines): Synthesis and structural studies of zinc(II), copper(II) and nickel(II) complexes

The synthesis, crystal structures, magnetic and spectroscopic properties of zinc(II), nickel(II) and copper(II) dinuclear complexes 2-4 of a novel dinucleating polyoxazoline ligand 1 are reported. X-ray analysis revealed that the three complexes are centrosymmetric dinuclear species with an overall S shape, the bisoxazoline moieties pointing toward the aromatic core of the molecule. Magnetic susceptibility measurements suggest that there is a very weak exchange interaction between the copper or nickel ions in complexes 3 and 4.     

Transition metal-saccharide chemistry: d-glucose complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)

Metal complexes of d-glucose (d-Glc) from large cation containing dibromo-dichloro salts of dipositive metals [NEt₄]₂[MBr₂Cl₂] (M = Mn, Co, Ni, Cu and Zn) and the disodium salt of glucose were synthesized from a MeOH:MeCN mixture. The complexes were characterized by UV-vis absorption, circular dichroism, IR and proton magnetic resonance spectroscopies, and by elemental analysis, and were found to be Na[M(d-Glc)(OMe)Cl]. Cyclic voltammetric studies of these complexes, in the acidic to neutral pH range, indicated no dissociation, even in highly acidic conditions.This paper is dedicated to Professor Richard H. Holm (Harvard University) on the occasion of his 60th birthday.     

Adsorption of Cu(II), Ni(II) and Zn(II) on modified jute fibres

The potential of a lignocellulosic fibre, jute, was assessed for adsorption of heavy metal ions like Cu(II), Ni(II) and Zn(II) from their aqueous solutions. The fibre was also used as adsorbent after chemically modifying it by two different techniques viz, loading of a dye with specific structure, C.I. Reactive Orange 13, and oxidising with hydrogen peroxide. Both the modified jute fibres gave higher metal ion adsorption. Thus, the dye loaded jute fibres showed metal ion uptake values of 8.4, 5.26 and 5.95 mg/g for Cu(II), Ni(II) and Zn(II), respectively, while the corresponding values for oxidised jute fibres were 7.73, 5.57 and 8.02 mg/g, as against 4.23, 3.37 and 3.55 mg/g for unmodified jute fibres. Adsorption isotherm models indicated best fit for Langmuir model for the modified jute fibres. The adsorption values decreased with lowering of pH. The desorption efficiency, regenerative and reuse capacity of these adsorbents were also assessed for three successive adsorption-desorption cycles. The adsorptive capacity was retained only when the caustic soda regeneration is carried out as an intermediate step after desorption. Possible mechanism has been given.     

Dipicolinato complexes of cobalt(II), copper(II) and zinc(II) with thiamine dications

Cobalt(II), copper(II) and zinc(II) dipicolinato complexes having thiamine dication with compositions [HT][CoL₂]·5H₂O (1), [HT][CuL₂]·5H₂O (2) and [HT][ZnL₂]·5H₂O (3) (L = dipicolinato anion, T = thiamine cation) are synthesized, characterized by X-ray diffraction and other spectroscopic techniques. The thiamine part in these complexes exists as divalent cations. The second protonation of thiamine takes place at the less crowded nitrogen atom of the pyrimidine ring. These complexes are stabilized by electrostatic and hydrogen-bonding interactions of -N⁺-H and -COO⁻ groups along with crystallized water molecules. The complexes are stable in solution as determined by ¹H NMR and visible study. The complex 1 has two medicinal components which can be easily separated by controlling pH in aqueous medium. It gets decomposed on treatment with sodium hydroxide at pH > 8 to form neutral complex {[Na₂(μ-H₂O)₃(H₂O)₃][CoL₂]·H₂O}₂.