Spring Time and Autumn Time Toxic Effects of Copper (II), 3-(2-Furyl) Prop-2-Enal Semicarbazone and [CuCl2(FASC)2] Complex in Mice

In vitro, 3-(2-furyl) prop-2-enal semicarbazone-copper (II) complex [CuCl₂(FASC)₂] presents antimitotic effects. In this work we studied the in vivo seasonal toxic effects in male Swiss mice of CuCl₂, and FASC and the [CuCl₂(FASC)₂] complex. In spring, one injection of CuCl₂8.10^-2 mmol killed 16% of animals after 24 h. Cupric chloride lethal dose was up to 64.10^-2 mmol with 100% mice dead after 24 h. FASC was well tolerated from 0.65 to 1.3 mmol. The complex was 100% lethal with 48.10^-2 mmol. In autumn, mice were more sensitive to CuCl₂ and to the complex with lethal doses up to 32.10^-2 mmol and 8.10^-2 mmol, respectively. On the other hand, FASC was well tolerated. It is concluded that the in vivo toxic effects of CuCl₂ and [CuCl₂(FASC)₂] complex are quite different in spring and autumn.     

Chronotoxicity of a Copper (II) Complex with a Linear Tetradentate Ligand in Mice

In vitro copper (II) complex presents antimitotic effects. In this work, we have studied the in vivo seasonal toxic effects of copper (II), ligand (H₂L) and the complex [Cu(H₂L)(H₂O)₂]Cl₂·4H₂O in male Swiss mice. During spring, an i.p. injection of CuCl₂ in aqueous NaCl (9 g·l^-1) up to 0.05 µmol·kg^-1 b.w. (body weight) killed 60% of the rodents after 6 days. LD100 was up to 0.3 µmol·kg^-1; H₂L was well tolerated, while the complex was 30% lethal with 50 µmol·kg^-1. In autumn, mice were less sensitive to CuCl₂, and both ligand and complex were equally tolerated and this leads to the conclusion that, in vivo, chronotoxicities of copper (II) and complex in NaCl aqueous solutions are quite different in spring and autumn seasons.     

Chronotolerance of a Nickel (II) Complex with the 5-Methyl 2-Furaldehyde Thiosemicarbazone Ligand in Male Swiss Mice

In vitro nickel (II) complex presents antimitotic effects. In this work, we have studied the in vivo seasonal effects of nickel (II), ligand and the complex [NiCl₂(M5FTSC)₂] in male Swiss mice. During spring, an intra peritoneal (i.p.) injection of NiCl₂ in aqueous NaCl up to 1.0.10^-2 mmol.kg^-1 body weight (b.w.) killed 10% of the rodents after 6 days. Lethal dose 100% (LD100) was up 1.91.10^-2 mmol.kg^-1 b.w.; ligand was less toxic than Ni (II), while the complex was 25% lethal at 1.37.10^-2 mmol.kg^-1 b.w. In autumn, mice were less sensitive to NiCl₂. The ligand and the complex, on the contrary, were more toxic. This leads us to the conclusion that, in vivo, chronotolerance of nickel (II), ligand and complex in aqueous solution, are quite different in spring and autumn seasons.     

Synthesis,characterization and DNA-binding properties of novel dipyridophenazine complex of ruthenium (II) : [Ru(IP)2(DPPZ)]2+

A novel ruthenium(II) complex of dipyridophenazine (DPPZ) with the ancillary ligand imidazole[4,5-f] [1,10]phenanthroline (IP), [Ru(IP)₂(DPPZ)] (PF₆)₂, has been synthesized and characterized by elemental analysis, 1D and 2D ¹H NMR, fast-atom bombardment mass spectra (FABMS), electronic spectroscopy and cyclic voltammetry. The DNA-binding properties of the complex were studied by spectroscopic methods. The intrinsic binding constant, K =2.1 × 10⁷M⁻¹, of the complex to calf thymus DNA has been determined by absorption titration in 5 mmol dm⁻³ Tris-HCl, 50 mmol dm⁻³ NaCl buffer (pH 7.0). The excited state lifetimes and luminescence quenching with [Fe(CN)₆]⁴⁻ as the quencher in the presence of DNA were also tested and mono-exponentiality was observed for the emission decay curves. Viscosity measurements together with the optical titrations unambiguously proved that the complex bound with DNA intercalatively and that the binding affinity to DNA was several times larger than that of the parent complex [Ru(bpy)₂(DPPZ)]²⁺.     

Synthesis and characterization of new unsaturated macrobicyclic and bis(macrocyclic) copper(II) complexes containing N-CH2-N linkages

New copper(II) complexes [CuL²]²⁺ (L²=7,7,9-trimethyl-1,3,6,10,13-pentaazabicyclo[11,2,1^1.13]hexadec-9-ene) and [Cu₂(L³)(H₂O)₂]⁴⁺ have been prepared by the reaction of [CuL¹]²⁺ (L¹=5,5,7-trimethyl-1,4,8,11,14-pentaazatetradce-7-ene) and formaldehyde. The mononuclear complex [CuL²]²⁺ has a square-planar coordination geometry with a 5-6-5-6 chelate ring sequence and is relatively stable even in low pH at room temperature. The dinuclear complex [Cu₂(L³)(H₂O)₂]⁴⁺ consists of two unsaturated 15-membered pentaaza macrocyclic units (7,7,9-trimethyl-1,3,6,10,13-pentaazacyclopentadec-9-ene) that are linked together by a methylene group in a tilted face-to-face arrangement [Cu?Cu distance: 7.413(2) Å ]. Each macrocyclic unit of [Cu₂(L³)(H₂O)₂]⁴⁺ contains one four-membered chelate ring and has a severely distorted octahedral coordination polyhedron. The dinuclear complex is quite stable in aqueous solutions containing an excess of formaldehyde or in dry acetonitrile but is decomposed to [CuL¹]²⁺ and [CuL²]²⁺ in pure water.     

Chronotoxicity of a Copper (II) Complex with a Linear Tetradentate Ligand in Mice

In vitro copper (II) complex presents antimitotic effects. In this work, we have studied the in vivo seasonal toxic effects of copper (II), ligand (H₂L) and the complex [Cu(H₂L)(H₂O)₂]Cl₂·4H₂O in male Swiss mice. During spring, an i.p. injection of CuCl₂ in aqueous NaCl (9 g·l^-1) up to 0.05 µmol·kg^-1 b.w. (body weight) killed 60% of the rodents after 6 days. LD100 was up to 0.3 µmol·kg^-1; H₂L was well tolerated, while the complex was 30% lethal with 50 µmol·kg^-1. In autumn, mice were less sensitive to CuCl₂, and both ligand and complex were equally tolerated and this leads to the conclusion that, in vivo, chronotoxicities of copper (II) and complex in NaCl aqueous solutions are quite different in spring and autumn seasons.     

Further studies on the coordination chemistry of [Pt2(μ-S)2(PPh3)4] towards indium(III) substrates

The reactivity of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] towards a variety of indium(III) substrates has been explored. Reaction with excess In(NO₃)₃ and halide (KBr or NaI) gave the four-coordinate adducts [Pt₂(μ-S)₂(PPh₃)₄InX₂]⁺[InX₄]⁻ (X = Br, I). An X-ray structure determination on the iodo complex revealed a slightly distorted tetrahedral coordination geometry at indium. In contrast, reaction of [Pt₂(μ-S)₂(PPh₃)₄] with indium(III) chloride was more complex; the ion [Pt₂(μ-S)₂(PPh₃)₄InCl₂]⁺ was initially observed in solution (using ESI mass spectrometry), and isolated as its BPh₄⁻ salt. Analysis of [Pt₂(μ-S)₂(PPh₃)₄InCl₂]⁺[BPh₄]⁻ by ESI MS showed the parent cation when analysed in MeCN solution. However in solutions containing methanol, partial solvolysis occurred to give the di-indium species [{Pt₂(μ-S)₂(PPh₃)₄InCl(OMe)}₂]²⁺ (proposed to contain an In₂(μ-OMe)₂ unit with five-coordinate indium) and its fragment ion [Pt₂(μ-S)₂(PPh₃)₄InCl(OMe)]⁺. Reaction of [Pt₂(μ-S)₂(PPh₃)₄] with InCl₃·3H₂O, 8-hydroxyquinoline (HQ) and trimethylamine in methanol gave the adduct [Pt₂(μ-S)₂(PPh₃)₄InQ₂]⁺, isolated as its PF₆⁻ salt. The same cationic complex is formed when [Pt₂(μ-S)₂(PPh₃)₄] is reacted with InQ₃ in methanol, but in this case the product is contaminated with the mononuclear complex [(Ph₃P)₂PtQ]⁺ formed by disintegration of the trinuclear complex [Pt₂(μ-S)₂(PPh₃)₄InQ₂]⁺ with byproduct Q⁻. [(Ph₃P)₂PtQ]⁺BPh₄⁻ was independently prepared from cis-[PtCl₂(PPh₃)₂] and HQ/Me₃N, and is the first example of a platinum 8-hydroxyquinolinate complex containing phosphine ligands.     

Two new copper(II) polyamine compounds: Synthesis, characterization and crystal structure

Two new compounds of Cu(II) of stoichiometry CuCl₄(polyamineH₂) containing the polyamines (PA): spermidine or spermine were prepared. Their synthesis, spectroscopic and structural characterization are herein described. The obtained complex with spermidine was characterized by elemental and thermogravimetric analysis, electronic and infrared spectroscopy. In the case of the compound with spermine, crystals were obtained. So, beside all other techniques the compound was also characterized by single crystal X-ray diffractometry. In both cases the species [CuCl₄]²⁻ is present and displays a similar polymeric structure. The X-ray, infrared and electronic spectra are herein discussed based on structural peculiarities of the compounds.     

Cyano-bridged cluster-metal coordination compound: synthesis and crystal structure of [Cu(NH3)3][Cu(NH3)4][Cu(NH3)5][W4Te4(CN)12]·5H2O

Dark-brown single crystals of the title compound 1 were obtained in high yield by layering a CuCl₂ solution in 25% aqueous ammonia on a glycerol solution of K₆[W₄Te₄(CN)₁₂]·5H₂O. The complex 1 was characterized by single crystal X-ray diffraction analysis and IR spectroscopy. The X-ray structure of 1 reveals a polymeric chain cyano-bridged cluster-metal coordination compound. The [W₄Te₄(CN)₁₂]⁶⁻ cluster anions are linked one to another by Cu²⁺ cations through coordination by nitrogen atoms of the CN groups.     

Study of Pt(II)-cyclic amines complexes of the types cis- and trans-Pt(amine)2I2 and cis- and trans-Pt(amine)2(NO3)2 and their aqueous products by

Complexes of the types cis- and trans-Pt(amine)₂I₂ containing cyclic amines were synthesized and studied mainly by IR and multinuclear NMR spectroscopies. The compounds were converted to cis- and trans-Pt(amine)₂(NO₃)₂, which were also investigated. The hydrolysis and the aquation reactions of the latter compounds were then studied in D₂O in different conditions of pH. In acidic medium, the aqueous product is [Pt(amine)₂(D₂O)₂]²⁺ and for a few amines, [Pt(amine)₂(D₂O)(NO₃)]⁺ was detected. In basic pH, the main product is Pt(amine)₂(OD)₂ and Pt(amine)₂(OD)(NO₃) was detected for several compounds. In neutral pH, the cis isomers form between two and four species in fresh solutions. The most shielded species in ¹⁹⁵Pt NMR is the monoaqua-monohydroxo complex cis-[Pt(amine)₂(D₂O)(OD)]⁺ and the less shielded compound is the dihydroxo-bridged dimer [Pt(amine)₂(μ-OD)₂Pt(amine)₂]²⁺, which were observed for all the compounds. For a few amines, the monohydroxo-bridged dimer [Pt(D₂O)(amine)₂(μ-OD)Pt(OD)(amine)₂]²⁺ was detected and for cyclohexylamine, a fourth signal was assigned to a cyclic hydroxo-bridged trimer [(Pt(amine)₂(μ-OD))₃]³⁺. ¹⁹⁵Pt NMR spectroscopy has shown that the concentration of the monomer decreases with time, while the concentration of the dimers increases. Only one product was observed for the trans isomers in neutral pH. The signal was assigned to the monoaqua-monohydroxo species trans-[Pt(amine)₂(D₂O)(OD)]⁺. The ¹³C and ¹H NMR spectra of most of the complexes were measured. All the coupling constants ^2,3J(¹⁹⁵Pt-¹H) and ^2,3J(¹⁹⁵Pt-¹³C) are larger in the cis compounds than in the trans isomers.     

Formation and structural chemistry of the unusual cyanide-bridged dinuclear species [Ru2(NN)2(CN)7] (NN = 2,2′-bipyridine or 1,10-phenanthroline)

Crystallisation of simple cyanoruthenate complex anions [Ru(NN)(CN)₄]²⁻ (NN = 2,2′-bipyridine or 1,10-phenanthroline) in the presence of Lewis-acidic cations such as Ln(III) or guanidinium cations results, in addition to the expected [Ru(NN)(CN)₄]²⁻ salts, in the formation of small amounts of salts of the dinuclear species [Ru₂(NN)₂(CN)₇]³⁻. These cyanide-bridged anions have arisen from the combination of two monomer units [Ru(NN)(CN)₄]²⁻ following the loss of one cyanide, presumably as HCN. The crystal structures of [Nd(H₂O)_5.5][Ru₂(bipy)₂(CN)₇] · 11H₂O and [Pr(H₂O)₆][Ru₂(phen)₂(CN)₇] · 9H₂O show that the cyanoruthenate anions form Ru-CN-Ln bridges to the Ln(III) cations, resulting in infinite coordination polymers consisting of fused Ru₂Ln₂(μ-CN)₄ squares and Ru₄Ln₂(μ-CN)₆ hexagons, which alternate to form a one-dimensional chain. In [CH₆N₃]₃[Ru₂(bipy)₂(CN)₇] · 2H₂O in contrast the discrete complex anions are involved in an extensive network of hydrogen-bonding involving terminal cyanide ligands, water molecules, and guanidinium cations. In the [Ru₂(NN)₂(CN)₇]³⁻ anions themselves the two NN ligands are approximately eclipsed, lying on the same side of the central Ru-CN-Ru axis, such that their peripheries are in close contact. Consequently, when NN = 4,4′-^tBu₂-2,2′-bipyridine the steric bulk of the t-butyl groups prevents the formation of the dinuclear anions, and the only product is the simple salt of the monomer, [CH₆N₃]₂[Ru(^tBu₂bipy)(CN)₄] · 2H₂O. We demonstrated by electrospray mass spectrometry that the dinuclear by-product [Ru₂(phen)₂(CN)₇]³⁻ could be formed in significant amounts during the synthesis of monomeric [Ru(phen)(CN)₄]²⁻ if the reaction time was too long or the medium too acidic. In the solid state the luminescence properties of [Ru₂(bipy)₂(CN)₇]³⁻ (as its guanidinium salt) are comparable to those of monomeric [Ru(bipy)(CN)₄]²⁻, with a ³MLCT emission at 581 nm.     

Structure and reactivity of [Ru(2,3-Medpp)2Cl2]

The structure and reactivity of the complex [Ru(2,3-Medpp)₂Cl₂](PF₆)₂ (2,3-Medpp⁺=2-[2-(1-methylpyridiniumyl)]-3-(2-pyridyl)pyrazine) was investigated by X-ray diffraction (XRD), ¹H NMR, redox, and UV-Vis absorption measurements. X-ray analysis shows that crystals obtained from an acetonitrile-toluene solution contain the trans-Cl₂, trans-pyrazine isomeric form, while ¹H NMR and redox measurements on the main product of the synthetic workup indicate the presence of the trans-Cl₂, cis-pyrazine isomer. In the dark at 70 °C, the complex [Ru(2,3-Medpp)₂Cl₂]²⁺ reacts slowly in acetonitrile isomerizing to the cis-[Ru(2,3-Medpp)₂(CH₃CN)Cl]³⁺ species. Under ambient light in the presence of excess AgNO₃ the cis-[Ru(2,3-Medpp)₂(CH₃CN)₂]⁴⁺ species is obtained.     

Syntheses, stereochemistry, reactivity, and some properties of sulfur-bridged cobalt(III)-cadmium(II) polynuclear complexes derived from mononuclear cobalt(III) complex with d-penicillaminate

A reaction of the octahedral bidentate metalloligand, trans(N)-[Co(d-pen)₂]⁻ (d-pen=d-penicillaminate) with Cd(NO₃)₂ or Cd(ClO₄)₂ gave a novel S-bridged trinuclear complex, [Cd(H₂O){Co(d-pen)₂}₂] (1). In this complex molecule, the central Cd atom is surrounded by four S atoms from two [Co(d-pen)₂]⁻ units and one O atom of a H₂O molecule to form a distorted five-coordinated geometry. Each of two terminal [Co(d-pen)₂]⁻ units takes an approximately octahedral geometry and has a similar trans(N) geometry to that of the starting material. On the other hand, the reaction of trans(N)-[Co(d-pen)₂]⁻ with CdCl₂ in the molar ratio of 1:1 gave an S-bridged dinuclear complex, [CdCl{Co(d-pen)₂}(H₂O)_m]·nH₂O (m+n=4) (2). The reactivity of trans(N)-[Co(d-pen)₂]⁻ toward CdCl₂ is significantly influenced by the ratio of two components, and the formation of a similar trinuclear species to 1 is also suggested under the condition with excess amount of trans(N)-[Co(d-pen)₂]⁻. Some spectrochemical properties of these complexes are also discussed in relation to their structures.     

The Effects of Grafting of 2-Pyridyl to [Ru(bpy)2(Hpip)]2+ on Acid-Base and DNA-Binding Properties: Experimental and DFT Studies

Abstract

A new Ru(II) complex of [Ru(bpy)₂(Hppip)]²⁺ {bpy = 2,2′-bipyridine; Hppip = 2-(4-(pyridin- 2-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline} has been synthesized by grafting of 2-pyridyl to parent complex [Ru(bpy)₂(Hpip)]²⁺ {Hppip = 2-(4-phenyl)-1H-imidazo[4,5-f] [1,10]phenanthroline}. The acid-base properties of [Ru(bpy)₂(Hppip)]²⁺ studied by UV-visible and luminescence spectrophotometric pH titrations, revealed off-on-off luminescence switching of [Ru(bpy)₂(Hppip)]²⁺ that was driven by the protonation/deprotonation of the imidazolyl and the pyridyl moieties. The complex was demonstrated to be a DNA intercalator with an intrinsic DNA binding constant of (5.56 ± 0.2) × 10⁵ M^?1 in buffered 50 mM NaCl, as evidenced by UV-visible and luminescence titrations, reverse salt effect, DNA competitive binding with ethidium bromide, steady-state emission quenching by [Fe(CN)₆]^4-, DNA melting experiments and viscosity measurements. The density functional theory method was also used to calculate geometric/electronic structures of the complex in an effort to understand the DNA binding properties. All the studies indicated that the introduction of 2-pyridyl onto Hpip ligand is more favorable for extension of conjugate plane of the main ligand than that of phenyl, and for greatly enhanced ct-DNA binding affinity accordingly.     

Synthesis,structural characterization and cell death-inducing effect of novel palladium(II) and platinum(II) saccharinate complexes with 2-(hydroxymethyl)pyridine and 2-(2-hydroxyethyl)pyridine on cancer cells in vitro

Four palladium(II) and platinum(II) saccharinate (sac) complexes with 2-(hydroxymethyl)pyridine (2-hmpy) and 2-(2-hydroxyethyl)pyridine (2-hepy), namely trans-[Pd(2-hmpy)₂(sac)₂]·H₂O (1), trans-[Pt(2-hmpy)₂(sac)₂]·3H₂O (2), trans-[Pd(2-hepy)₂(sac)₂] (3) and trans-[Pt(2-hepy)₂(sac)₂] (4), have been synthesized and characterized by elemental analysis, UV–vis, IR and NMR. Single crystal X-ray analysis reveals that the metal(II) ions in each complex are coordinated by two sac and two 2-hmpy or 2-hepy ligands with a trans arrangement. Anticancer effects of 1–4 were tested against four different cancer cell lines (A549 and PC3 for lung cancer, C6 for glioblastoma, and Hep3B for liver cancer). Cytotoxicity was first screened by the MTT assay and the results were further confirmed by the ATP assay. The mode of cell death was determined by both histological and biochemical methods. Among the metal complexes, complex 2 resulted in relatively stronger anti-growth effect in a dose-dependent manner (3.13–200 μM), compared to the others, by inducing apoptosis.     

Synthesis and characterisation of palladium(II) and platinum(II) compounds containing pyrazole-derived ligands: crystal structure of [PdCl2(HL)] (HL = 3-phenyl-5-(2-pyridyl)pyrazole)

Reaction of the ligands 3-phenyl-5-(2-pyridyl)pyrazole (HL¹), 3,5-bis(2-pyridyl)pyrazole (HL²), 3-methyl-5-(2-pyridyl)pyrazole (HL³) and 3-methyl-5-phenylpyrazole (HL⁴) with [MCl₂(CH₃CN)₂] (M = Pd(II), Pt(II)) or [PdCl₂(cod)] gives complexes with stoichiometry [PdCl₂(HL)₂] (HL = HL¹, HL², HL³), [Pt(L)₂] (L = L¹, L², L³) and [MCl₂(HL⁴)₂] (M = Pd(II), Pt(II)). The new complexes were characterised by elemental analyses, conductivity measurements, infrared and ¹H NMR spectroscopies. The crystal and molecular structure of [PdCl₂(HL¹)] was resolved by X-ray diffraction, and consists of monomeric cis-[PdCl₂(HL¹)] molecules. The palladium centre has a typical square planar geometry, with a slight tetrahedral distortion. The tetra-coordinated metal atom is bonded to one pyridine nitrogen, one pyrazolic nitrogen and two chloro ligands in a cis disposition. The ligand HL¹ is not completely planar.     

Synthesis and characterization of [Co(NO2)2(acac)(IMH2py)] with one-electron-reduced imino nitroxide radical associated with unusual displacement of acetylacetonate in the starting complex trans-Na[Co(NO2)2(acac)2]

A reaction of trans-Na[Co(NO₂)₂(acac)₂] with IM2py(2(2^′-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl) in methanol afforded trans-[Co(NO₂)₂(acac)(IMH2py)](IMH2py=1-hydroxyl-2(2^′-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole); one-electron reduction of the N-O radical moiety in IM2py and displacement of one of the two acac ligands with retention of two nitrito ligands in the starting complex during the reaction. This new complex was characterized by UV-Vis, ¹H NMR spectra and X-ray analysis.     

Synthesis and spectroscopic properties of some new seven-coordinate thioacetamide complexes of molybdenum(II) and tungsten(II)

The compounds [MI₂(CO)₃(NCMe)₂] (M = Mo or W) react with one equivalent of SC(NH₂)Me in CH₂Cl₂ at room temperature to initially give the acetonitrile substituted products [MI₂(CO)₃(NCMe)- {SC(NH₂)Me}] which was isolated for M = W. However, the molybdenum complex rapidly dimerizes with loss of acetonitrile to give the iodide-bridged compound [Mo(σ-I)I(CO)₃ {SC(NH₂)Me}]₂. The tungsten complex does not appear to dimerize, even after stirring at room temperature for 72 h in CH₂Cl₂. Two equivalents of thioacetamide react with [MI₂- (CO)₃(NCMe)₂] in CH₂Cl₂ at room temperature to give the new bisthioacetamide compounds [MI₂- (CO)₃{SC(NH₂)Me}₂] via displacement of the labile acetonitrile ligands. The low temperature (−70 °C) ¹³C NMR spectrum of [WI₂(CO)₃{SC(NH₂)Me}₂] indicates that the geometry of the complex is capped octahedral with a carbonyl ligand in the unique capping position.     

Hydroxylation of a methyl group: synthesis of [Cu2(btmmO)2I] and of [Cu2(btmmO)2] containing the novel ligand {bis(trimethylmethoxy)guanidino}propane (btmmO) by copper-assisted oxygen activation

The reaction of the bisguanidine copper(I) compounds [Cu(btmgp)I] and [Cu₂(btmgp)₂][PF₆]₂ with molecular oxygen afforded at low temperatures complexes containing the bis-μ-oxo dicopper(III) core, which is capable to hydroxylate one of the N-CH₃-groups of the {bis(tetramethyl)guanidino}propane ligands. The formation of the novel ligand {bis(trimethylmethoxy)guanidino}propane (btmmO) is reported as it represents the first hydroxylation of a N-methyl group. The products of this reaction are novel alkoxo-bridged binuclear copper complexes, namely [Cu₂(btmmO)₂I]⁺ containing an iodide ion in a novel bridging situation, as well as [Cu₂(btmmO)₂]²⁺ which have been identified in their complex salts and [Cu₂(btmmO)₂][PF₆]₂ · 2MeCN, respectively. Concomitantly, the hydroxo-bridged binuclear copper compounds [Cu₂(btmgp)₂(μ-OH)₂]I₂ and [Cu₂(btmgp)₂(μ-OH)₂][PF₆]₂ are formed as couple products. The formation of the bis-μ-oxodicopper(III) complexes was monitored by UV/Vis-spectroscopy, and the reaction products were characterised by X-ray diffraction, vibrational spectroscopy and elemental analysis.     

Two forms of a copper(II) complex of 3-phenyl-5-(2-pyridyl)-4-(4-pyridyl)-4H-1,2,4-triazole: a six-coordinate monomer versus a five-coordinate polymer

The reaction of the new bidirectional ligand 3-phenyl-5-(2-pyridyl)-4-(4-pyridyl)-4H-1,2,4-triazole (pyppt) with Cu(ClO₄)₂ · 6H₂O in a 2:1 molar ratio in EtOH affords the complex [Cu^II(pyppt)₂(ClO₄)₂] · H₂O (1) as a microcrystalline turquoise solid. Recrystallisation of complex 1 from MeCN by vapour diffusion of Et₂O gives blue crystals of the monomeric octahedral complex [Cu^II(pyppt)₂(ClO₄)₂] · MeCN (2). In contrast, addition of EtOH to a solution of complex 1 in MeCN followed by slow evaporation yields blue crystals of the five-coordinate polymeric complex {[Cu^II(pyppt)₂](ClO₄)₂ · EtOH}_∞ (3). The structures of both complexes have been determined by single crystal X-ray diffraction.