Cobalt Polypyridyl Complexes as Transparent Solution‐Processable Solid‐State Charge Transport Materials

Charge transport materials (CTMs) are traditionally inorganic semiconductors or metals. However, over the past few decades, new classes of solution‐processable CTMs have evolved alongside new concepts for fabricating electronic devices at low cost and with exceptional properties. The vast majority of these novel materials are organic compounds and the use of transition metal complexes in electronic applications remains largely unexplored. Here, a solution‐processable solid‐state charge transport material composed of a blend of [Co(bpyPY4)](OTf)₂ and Co(bpyPY4)](OTf)₃ where bpyPY4 is the hexadentate ligand 6,6′‐bis(1,1‐di(pyridin‐2‐yl)ethyl)‐2,2′‐bipyridine and OTf^? is the trifluoromethanesulfonate anion is reported. Surprisingly, these films exhibit a negative temperature coefficient of conductivity (dσ/dT) and non‐Arrhenius behavior, with respectable solid‐state conductivities of 3.0 S m^?1 at room temperature and 7.4 S m^?1 at 4.5 K. When employed as a CTM in a solid‐state dye‐sensitized solar cell, these largely amorphous, transparent films afford impressive solar energy conversion efficiencies of up to 5.7%. Organic–inorganic hybrid materials with negative temperature coefficients of conductivity generally feature extended flat π‐systems with strong π–π interactions or high crystallinity. The lack of these features promotes [Co(bpyPY4)](OTf)_{2+ x} films as a new class of CTMs with a unique charge transport mechanism that remains to be explored.     

Advances in imaging of understudied ions in signaling: A focus on magnesium

The study of metal ions in the context of cell signaling has historically focused mainly on Ca²⁺, the second messenger par excellence. But recent studies support an emerging paradigm in which other metals, including magnesium and d-block metals, play a role in signal transduction as well. Armed with the right indicators, fluorescence microscopy offers a unique combination of spatial and temporal resolution perfectly suited to reveal metal transients in real time, while also helping identify possible sources of ion mobilization and molecular targets. With a focus on Mg²⁺, we highlight recent advancements in the development of molecular indicators and imaging strategies for the study of metal ions in signaling. We discuss remaining conceptual and technical challenges in the field, and we illustrate through the case of Mg²⁺ how the study of nontraditional ions in signaling is inspiring technological developments applicable more broadly to the study of metals in biology.     

Cu2+ and Ni2+ interactions with N-terminal fragments of Hpn and Hpn-like proteins from Helicobacter pylori: unusual impact of poly-Gln sequence on the complex stability

The N-terminal protected and unprotected peptides MAHHEEQHG-NH₂, Ac-MAHHEEQHG-NH₂ from Hpn (Helicobacter histidine-rich protein) and MAHHEQQQQQQA-NH₂, Ac-MAHHEQQQQQQA-NH₂ from Hpn-like protein, respectively, were synthesized and their interactions with Cu²⁺ and Ni²⁺ ions were studied by potentiometric, UV-visible, CD, and EPR techniques. The studies have shown that because of their albumin-like sequence, unprotected peptides are very effective chelating agents for both studied metals. The presence of the hexa-glutamine sequence has very distinct impact on the stability of the complexes formed even if direct interactions with metal ions were not found. The much more effective Ni²⁺ binding by Hpn-like N-terminal domain when compared to Hpn protein could be critical for different biological functions played by both proteins.     

Synthesis and chemical characterization of Cu, Ni and Zn complexes of 3,5-bis(2′-pyridyl)-1,2,4-oxadiazole and 3-(2′-pyridyl)5-(phenyl)-1,2,4-oxadiazole ligands

The synthesis and structural characterization of Ni^II, Cu^II and Zn^II complexes of two chelating 1,2,4-oxadiazole ligands, namely 3,5-bis(2′-pyridyl)-1,2,4-oxadiazole (bipyOXA) and 3-(2′-pyridyl)5-(phenyl)-1,2,4-oxadiazole (pyOXA), is here reported. The formed hexacoordinated metal complexes are [M(bipyOXA)₂(H₂O)₂](ClO₄)₂ and [M(pyOXA)₂(ClO₄)₂], respectively (M = Ni, Cu, Zn). X-ray crystallography, ¹H and ¹³C NMR spectroscopy and C, N, H elemental analysis data concord in attributing them an octahedral coordination geometry. The two coordinated pyOXA ligands assume a trans coplanar disposition, while the two bipyOXA ligands are not. The latter result is a possible consequence of the formation of H-bonds between the coordinated water molecules and the nitrogen atom of the pyridine in position 5 of the oxadiazole ring. The expected splitting of the d metal orbitals in an octahedral ligand field explains the observed paramagnetism of the d⁸ and d⁹ electron configuration of the nickel(II) and copper(II) complexes, respectively, as determined by the broadening of their NMR spectra.     

Spectrophotometric kinetic study and analytical implications of the glucose oxidase-catalyzed reduction of [MIII(LL)2Cl2]+ complexes by d-glucose (M=Os and Ru, LL=2,2′-bipyridine and 1,10-phenanthroline type ligands)

 Glucose oxidase-catalyzed reduction of cis[M^III (LL)₂Cl₂]⁺ (M=Os and Ru) complexes to cis[M^II (LL)₂Cl₂] (LL=2,2′-bipyridine and 1,10-phenanthroline type ligands) by d-glucose is a first-order process in the complex and the enzyme in aqueous buffered solution. The reaction follows MichaelisMenten kinetics in d-glucose and the rate is independent of d-glucose concentration above 0.03 M. The reactivity decreases in the series [Ru(bpy)₂Cl₂]⁺ > [Os(phen)₂Cl₂]⁺ > [Os(4,4′-Me₂bpy)₂Cl₂]⁺ > [Os(4,7Me₂phen)₂Cl₂]⁺. The measured second-order rate constant for the oxidation of reduced glucose oxidase by [Os(phen)₂Cl₂]⁺ in air equals 1.2×10⁵ M^–1 s^–1 at pH 6.7, [d-glucose] 0.05 M, and 25  °C, which is ca. 20% less than that when the reaction solutions are purged with argon. In the case of [Ru(bpy)₂Cl₂]⁺ the rate constant equals 1.8×10⁵ M^–1 s^–1 under similar conditions in air, showing higher reactivity of Ru complexes compared with Os ones. The reduction is pH-dependent with a maximum around 7. Added for solubilization of poorly soluble metal complexes, surfactants decrease the rates of the enzymatic reaction. The retardation effect increases in the series: cetyltrimethylammonium bromide < Triton X-100 < sodium dodecyl sulfate, i.e. on going from positively charged to neutral and then to negatively charged surfactants. The behavior of the Os^III and Ru^III complexes toward reduced glucose oxidase contrasts to that of recently studied ferricenium cations. As opposed to the latter, the former do not show kinetically meaningful binding with the enzyme, and the Michaelis kinetics typical of the ferricenium case is not realized for the Os^III, and Ru^III species. The systems Os^III- or Ru^III-glucose oxidase are convenient for routine "one pot" spectrophotometric monitoring of the d-glucose content in samples, since the metal reduction to M^II is accompanied by a strong increase in absorbance in the visible spectral region. Received: 1 July 1998 / Accepted: 13 January 1999     

Modification of aminoallenylidene complexes of chromium via exchange of the C3-bound amino group

The aminoallenylidene(pentacarbonyl)chromium complexes [(CO)₅CrCCC(NR¹R²)Ph] (1a-c) react with dimethylamine by addition of the amine to the C1C2 bond of the allenylidene ligand to give alkenyl(amino)carbene complexes [(CO)₅CrC(NMe₂)CHC(NR¹R²)Ph] (2a-c) (R¹ = Me: R² = Me (a), Ph (b); R¹ = Et: R² = Ph (c)). In contrast, addition of a large excess (usually 20 equivalents) of ammonia or primary amines, H₂NR, to solutions of [(CO)₅CrCCC(NMe₂)Ph] (1a) affords the aminoallenylidene complexes [(CO)₅CrCCC(NHR)Ph] (1d-w) in which the dimethylamino group is replaced by NH₂ or NHR, respectively. In addition to simple amines such as methylamine, butylamine, and aniline, amines carrying a functional group (allylamine, propargylamine) and amino acid esters as well as amino terpenes and amino sugars can be used to displace the NMe₂ substituent. Usually the Z isomer (with respect to the partial C3-N double bond) is formed exclusively. Products derived from addition of H₂NR to the C1C2 bond of 1a are not observed. The amino group in 1d-w is rapidly deprotonated by excess of amine to form iminium alkynyl chromates [1d-w]⁻, thus protecting 1d-w from addition of free amine to either C3 or across the C1C2 bond. The iminium alkynyl chromates are readily reprotonated by acids or by chromatography on wet SiO₂ to reform 1d-w.     

Polypyrazolates of the heavier group 13 and 14 elements: A review

Heavy group 13 and 14 analogs of the poly(pyrazolyl)borates are the subject of this review. Within these, the most extensive research has been performed on the study of polypyrazolylgallates Me₂Ga(R₂pz)₂]⁻ (R = H or Me) and [MeGa(pz)₃]⁻, and their complexes with transition metals. In this review, the common features shared with the boron analogs are presented and contrasted. Other recently reported series of group 13 analogs are the alkali polypyrazolylaluminates Na[(R₂pz)₃] with R = Me, ^tBu; R′ = M. The complexes with one or two pyrazolyl ligands on aluminum display anagostic Al-CH₃?Na interactions, these interactions are persistent even if complexes were obtained from solutions with THF that normally coordinate alkali ions. The polypyrazolylsilane ligands Me₂Si(R₂pz)₂ and MeSi(R₂pz)₃ with R = H, Me are remarkably easy to obtain and isolate, in contrast is the fact that the carbon analogs are much harder to obtain and isolate in reasonable yields. Therefore it is surprising that the chemistry of the former ligands is not as developed as could be anticipated. Nevertheless there are examples of the use of these silanes as ligands with the following transition metals: Cr, Mn, Cu, Zn, Sc and Zr. The heavier group 14 analogs with Ge and Sn display coordination patterns with alkali and alkaline ions that resemble those observed with the borates and aluminates. The formation of cationic bimetallic cages of the type [E₂(R₂pz)₃]⁺ and neutral complexes [E₂(R₂pz)₄] has also been observed that can be consider formal isomers of the alkenes. The use of these compounds as ligands has been recently reported.     

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.     

Iron-iron interaction through an ethanedithiolate ligand: a magnetic and theoretical study

The compound ([CpFe(dppe)]₂[μ-SCH₂CH₂SS,S′])(PF₆)₂ ([1][PF₆]₂) has been synthesized and its magnetic properties have been investigated by susceptometer quantum interface device (SQUID) measurements in the temperature range 5-300 K. The d⁵-d⁵1²⁺ complex exhibits intramolecular antiferromagnetic behavior, with a magnetic coupling constant of −6.4 cm⁻¹. Density functional theory (DFT) calculations on a model of 1²⁺ (as well as on models of 1⁺ and 1) allow to determine its molecular structure and analyse its bonding and magnetic properties. The computed spin density exhibits significant localization on both the Fe and S centers. Replacing the heteroatoms of the bridging ligand by CH₂ groups leads to a relocalization of the spin density on the metal atoms and favors ferromagnetic coupling.     

Synthesis, characterisation and crystal structure of hydroxylamido-κN,O(iodo)[tris(3,5-dimethylpyrazol-1-yl)borato]nitrosylmolybdenum(II)

The unusual 18e seven-coordinate Mo(II) complex [Mo(NO)(H₂NO-κ²N,O)(Tp^Me2)I] (1; [Tp^Me2]⁻ is hydrotris(3,5-dimethylpyrazol-1-yl)borate) has been synthesised and characterised by IR, ¹H NMR and ESI-MS spectroscopies and by a single crystal X-ray diffraction study. The complex has a distorted pentagonal bipyramid structure with equatorial κ²-NH₂O⁻ ligand (d_N-O = 1.387 Å, d_Mo-N and d_Mo-O equal 2.049 and 2.092 Å, respectively). In the solid state 1 exists as a dimer (the point group C_i) due to the formation of two NH?O hydrogen bonds (d_N-H?O = 2.064 Å) between the adjacent NH₂O⁻ ligands, whilst in solution at/or above RT it resolves itself giving a monomer, which readily isomerises to more thermodynamically stable diastereoisomer.     

1,3-Dipolar cycloaddition to the FeSC fragment 20. Preparation and properties of carbonyliron complexes of di-thiooxamide. Reactivity of the mononuclear (di-thiooxamide)Fe(CO)3 towards dimethyl acetylenedicarboxylate

Reaction of Fe₂(CO)₉ at room temperature in THF with the di-thiooxamides (L), SC{N(R,R′)}C{(R,R′)N}S [R=Me, R′-R′=(CH₂)₂ (a); R=H, R′=ⁱPr (b); R=H, R′=iPr (c), R=H, R′=benzyl (d); R=H, R′=H (e)], results for ligands a-d initially in the formation of the mononuclear σ-S, σ-S′ chelate complexes Fe(CO)₃(L) (7a-d), which could be isolated in case of 7a and 7d. Under the reaction conditions, complexes 7a-d react further with [Fe(CO)₄] fragments to give three types of Fe₂(CO)₆(L) complexes (8a-d) in high yields, depending on the di-thiooxamide ligand used together with traces of the known complex S₂Fe₃(CO)₉ (14). The molecular structures of these complexes have been established by the single crystal X-ray diffraction determinations of 8a, 8b and 8d. In the reaction with ligand e the corresponding complex 7e was not detected and the well-known complexes 14 and S₂Fe₃(CO)₉ (15) were isolated in low yield. In situ prepared 7a reacts in a slow reaction with 1 equiv. of dimethyl acetylene dicarboxylate in a 1,3-dipolar cycloaddition reaction to give the stable initial ferra [2.2.1] bicyclic complex 10a in 60% yield. In complex 10a an additional Fe(CO)₄ fragment is coordinated to the sulfido sulfur atom of the cycloadded FeSC fragment. When a toluene solution of 10a is heated to 50 °C it loses two terminal CO ligands to give the binuclear FeFe bonded complex 11a in almost quantitative yield. The molecular structures of 10a and 11a have been confirmed by single crystal X-ray diffraction. Reaction of 7d at room temperature with 2 equiv. of dimethyl acetylene dicarboxylate results in the mononuclear complex 12d in 5% yield. The molecular structure of 12b has been established by single crystal X-ray diffraction and comprises a tetra dentate ligand with two ferra-sulpha cyclobutene, and a ferra-disulpha cyclopentene moiety. When the reaction is performed at 60 °C a low yield of 2,3,4,5-thiophene tetramethyl tertracarboxylate is obtained besides complex 12d.     

A new example of a tetranuclear iron(III) cluster containing the [Fe4O2] core: preparation, X-ray crystal structure, magnetochemistry and Mössbauer study of [Fe4O2(O2CMe)6(N3)2(phen)2]

Two synthetic procedures have been employed that allow access to the new tetranuclear cluster [Fe₄O₂(O₂CMe)₆(N₃)₂(phen)₂] (1), where phen is 1,10-phenanthroline. Complex 1 · 3MeCN displays an unusual structural asymmetry (observed for the second time) in its [Fe₄O₂]⁸⁺ core that can be considered as a hybrid of the bent (butterfly) and planar dispositions of four metal ions seen previously in such compounds with transition metals. Complex 1 has been characterized by variable-temperature magnetic susceptibility studies, and by IR and variable-temperature ⁵⁷Fe Mössbauer spectroscopies. Magnetochemical data reveal a diamagnetic ground state (S=0) with antiferromagnetic body-body and body-wingtip interactions between the iron(III) ions of the butterfly core (J_bb=−11 cm⁻¹, J_wb=−70 cm⁻¹). Magnetochemical and Mössbauer studies on 1 show that its structural asymmetry has practically no influence on these properties compared with the more symmetric types.     

Syntheses of linear-type S-bridged trinuclear complexes composed of heavy d metal ions and 2-aminoethanethiolate: comparative characterization by X-ray diffraction, spectroscopy and electrochemistry

The S-bridged trinuclear complexes composed of heavy d⁶ metal ions, [Rh^III{M(aet)₃}₂]³⁺ (M=Ir^III(1), Rh^III(2); aet = 2-aminoethanethiolate), have been prepared by the reactions of fac(S)-[M(aet)₃] with RhCl₃ · 3H₂O. The complexes were separated into meso (1a, 2a) and rac (1b, 2b) isomers by SP-Sephadex C-25 column chromatography. 1b and 2b were optically resolved by the column chromatographic method and characterized by CD spectroscopy. Crystal structures of 1a, 1b and 2a were determined by X-ray diffraction, and it was found that they consist of linear-type trinuclear structures. The central Rh(III) ion in the present complexes has d⁶ electronic configuration with the non-degenerated A-type cubic field term, and showed long Rh?M distances, acute S-M-S angles and obtuse Rh-S-M angles. These are in contrast with the complexes having the degenerated T-type cubic field term such as [M^′{M(aet)₃}₂]ⁿ⁺ (M^′=V^III, Mo^IV and Re^III, M=Ir^III, Rh^III, n=3 or 4). All the isomers have been comparatively characterized and discussed in solid state and the solution for spectrochemical and electrochemical properties.     

Influence of metal complexation on the metabolism of citrate byKlebsiella oxytoca

The uptake of ¹⁴C-labeled cadmium-, copper and zinc-citrate into cells of Klebsiella oxytoca was followed. The study was made in order to examine if the earlier reported disability of the bacterium to degrade these complexes was due to an inhibition in transport through the cell membrane. Citrate complexed to cadmium, copper or zinc was taken up at a similar rate to the free citric acid. However, the metal-citrate complexes were not metabolized as shown by the marked accumulation of ¹⁴C in the cells as compared with the ¹⁴C content in the cells incubated with free citric acid. This was confirmed by the results from trichloroacetic acid-precipitation showing that no ¹⁴C was incorporated into macromolecules when the citrate was complexed to the different metals. It is suggested that the inhibited degradation was due to effects on the interaction between enzyme (aconitase) and substrate in the conversion of citrate to iso-citrate. The role of complex configuration on the mineralization of metal-citrate is discussed and also tested in mineralization studies of other metal-citrate complexes (aluminum-, calcium-, cobalt-, manganese- and nickel-citrate).     

C-H activation by a terminal imidoiron(III) complex to form a cyclopentadienyliron(II) product

Imido complexes of the late transition metals have the ability to activate C-H bonds through the abstraction of hydrogen atoms from hydrocarbons. This paper describes the apparent hydrogen atom transfer from cyclopentadiene (CpH) to the isolable imidoiron(III) complex L^MeFeNAd (L^Me = 2,4-bis(2,6-diisopropylphenylimido)pent-3-yl; Ad = 1-adamantyl) in the presence of 4-tert-butylpyridine (^tBupy). The isolated product is not the amidoiron(II) complex, but instead it is L^MeFe(Cp)(^tBupy), the result of amido protonation by additional CpH. The crystal structures of both L^MeFeCp and L^MeFe(Cp)(^tBupy) are presented, and in the latter compound the Fe-C bonds are longer than in any previously characterized cyclopentadienyliron complex.     

CO substitution and diphosphine ligand chelation in the reaction between 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) and Re(2(CO)8(μ-H)(μ-η,η-C CPh)

The reaction between the redox-active diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) and the dirhenium compound Re₂(CO)₈(μ-H)(μ-η¹,η²-C CPh) in CH₂Cl₂ at room temperature proceeds by CO loss to give the dirhenium complex Re₂(CO)₇(bpcd)(μ-H)(η¹-C CPh) (1). This new complex was characterized in solution by IR and NMR (¹H and ³¹P) spectroscopy and in the solid state by X-ray diffraction analysis. Re₂(CO)₇(bpcd)(μ-H)(η¹-C CPh) crystallizes in the triclinic space group

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γ = 69.240(6)°, V = 2024.9(3) ų, Z = 2, d_calc = 1.862 g cm⁻³ R = 0.0221, R_w = 0.243 for 4066 observed reflections. The bpcd ligand in 1 adopts a chelating mode with a linear phenylacetylide ligand being located on the adjacent rhenium center cis to the bpcd ligand. This complex represents the first structurally characterized example of a hydrido-bridged dirhenium complex possessing both a linear acetylide ligand and a chelating diphosphine ligand.     

Structure, spectroscopic and magnetic properties of a novel 1-D coordination copper(II) polymer containing BIMAM ligand [BIMAM = bis(imidazol-2-yl)methylaminomethane] and μ-1,3 squarato bridges

This paper reports the synthesis and complete characterization (structural, spectroscopic and magnetic) of [Cu(HBIMAM)Cl(C₄O₄)]_n · (H₂O)_n [BIMAM = bis(imidazol-2-yl)methylaminomethane]. This compound is made of infinite chains - running along c axis - built from [CuCl(HBIMAM)]⁺ units bridged together by μ-O¹,O³-bis(monodentate) squarate anions. Non-covalent interactions (H-bonds and π-π) drive the build-up of an infinite three-dimensional array. The coordination polyhedron about the copper(II) ion is distorted square pyramidal. The EPR spectrum is indicative of a d_z²-y² ground state for the Cu(II) ions with significant contribution of d_z². Magnetic susceptibility measurements in the range 1.8-200 K show weak antiferromagnetic exchange interactions (2J = −3.5(1) cm⁻¹). The observed magnetic behaviour is discussed in terms of the crystal structure and compared with that observed in related copper(II) complexes containing μ-O¹,O³-squarato bridges.     

Antisymbiosis. Preferential coordination of anionic oxygen versus neutral sulfur donor atoms of methylsulfanyl- or methylsulfinyl-acetato, 2-benzoato and 2-phenolato to the cis-Pt(PPh3)2 and Pt(dppe) residues

The interaction of an excess of the title ligands L⁻ with the cis-Pt(phos)₂ moieties gives compounds a-bcis-[Pt(L-O)₂(phos)₂] (a, phos = P(Ph)₃; b, phos = 1/2 dppe), in which O- is preferred to S-coordination. Such preference is confirmed by the fact that the same products are obtained by reaction of excess of L⁻ with the previously reported a-d complexes [Pt(L-O,S)(phos)₂]⁺, (c, phos = PPh₃, d, phos = 1/2 dppe), for which chelate ring opening occurs with rupture of Pt-S rather than Pt-O bonds. Compound a can be obtained also by oxidative addition of HL to [Pt(PPh₃)₃]. The Pt-O bonds in compounds a-d are stable towards substitution by Me₂SO, pyridine and tetramethylthiourea. Substitution of L’s occurs with N,N′-diethyldithiocarbamate, which forms a very stable chelate with Pt(II). Thiourea and N,N′-dimethylthiourea also react, because they give rise to cyclometallated products [Pt(phos)₂(NRC(S)NHR)]⁺ (R = H, CH₃), with one ionised thioamido group, as revealed by an X-ray investigation of [Pt(PPh₃)₂(NHC(S)NH₂)]⁺. The preference of O versus S coordination, as well as the stability of the Pt-O bonds, are discussed in terms of antisymbiosis.     

Approach to a metallacycling polymerization — reactions of [(η-C5H5)Co(PPh3)2] with α,β-diynes and Me3SiCCC6H4C6H4CCSiMe3

Reactions of [CpCo(PPh₃)₂](Cp=η⁵-cyclopentadienyl) with conjugated diacetylenes were investigated in terms of the synthesis of π-conjugated organometallic polymers. The reaction of an α,β-diyne, PhCC---CCPh, gave three geometric isomers of dialkynylcobaltacyclopentadienes, 1a-c, and an insoluble polymeric product, 1d. A 2,4-dialkynyl complex, 2, and a 2,5-dialkynyl complex, 3, were obtained solely from Me₃SiCC---CCSiMe₃ and MeCC---CCMe, respectively. 1,1′-Bis(trimethylsilylethynyl)-4,4′-biphenyl afforded two isomers of 1,3-dialkynylcyclobutadiene complexes, 4a and 4b. The stability of the one-electron oxidized forms of the cobalacyclopentadiene and cyclobutadiene complexes was examined by cyclic voltammetry.     

Solubility and mobility of copper,zinc and lead in acidic environments

Understanding the chemical speciation of metals in solution is necessary for evaluating their toxicity and mobility in soils. Soil samples from the Powder River Basin, Wyoming were extracted with distilled deionised H₂O. Soil water extracts were subjected to chemical speciation to determine the relative distribution and chemical forms of copper (Cu), zinc (Zn) and lead (Pb) in acidic environments. As pyrite oxidised, the pH decreased from 6.6 to 2.4, concentration of dissolved sulfate (S_T) increased from 259 to 4,388 mg L^-1 and concentration of dissolved organic carbon (DOC) decreased from 56.9 to 14.4 mg L^-1. Dissolved Cu concentrations ranged from 0.06 to 0.42 mg L^-1 and dissolved Zn concentrations ranged from 0.084 to 4.60 mg L^-1. Dissolved concentrations of Pb were found to be 0.003 to 0.046 mg L^-1. Chemical speciation indicated that at near neutral pH, dissolved metal concentration in soil water extracts was dominated by DOC- metal complexes. At low pH, dissolved metal concentration in soil water extracts was dominated by free ionic forms (e.g. Cu²⁺, Zn²⁺, Pb²⁺) followed by ion pairs (e.g. CuSO₄ ⁰, ZnSO _inf4 ^sup0 , PbSO _in4 ^sup0 ). Results obtained in this study suggest that as soil pH decreased, the availability and mobility of metal ions increased due to the chemical form in which these metal ions are present in soil solutions.