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PubMed2006

High-valent iron complexes with tetraamido macrocyclic ligands: structures, Mössbauer spectroscopy, and DFT calculations.

Iron complexes of tetraamido macrocyclic ligands (TAML) are unique synthetic oxidation catalysts. In general, the central Fe(III) ion (S=3/2) is surrounded by four, almost planar, deprotonated amide-N sigma-donors although the full suite with new generation systems includes some substitution of amides with related donor functionalities. Oxidation under different conditions affords a variety of high-valent forms of iron-TAMLs. This review provides a summary and discussion of structural and spectroscopic features of complexes oxidized by one equivalent above the ferric state. These comprise Fe(IV)-TAML high spin (S=2) and intermediate spin (S=1) systems, wherein the oxidation equivalent can be taken from the metal (Fe(IV)) or the ligand (TAML radical-cation Fe(III)), and coupled spin (S=0) systems of mu-oxoiron(IV) dimers. The discussion is principally based on data obtained by X-ray crystallography, Mössbauer spectroscopy, and density functional theory calculations.

Iron↗

PubMed2006

A DFT overview of high-valent iron, cobalt and nickel tetraamidomacrocyclic ligand (TAML) complexes: the end of innocence?

Amidato-N ligands are normally viewed as classic, strongly sigma-donating, innocent ligands. However, when coordinated to high-valent transition metal centers, tetraamidomacrocyclic ligands are often substantially non-innocent, i.e., exhibit radical character involving the amido pi-systems. Even the so-called MAC* ligand, generally considered to be an innocent ligand, is non-innocent in several of its known complexes.

Cobalt↗

PubMed2005

Nitric oxide-dependent activation of pig oocytes: role of calcium.

Pig oocytes matured in vitro are parthenogenetically activated after treatment with nitric oxide (NO)-donor SNAP. The chelation of intracellular calcium ions with BAPTA-AM suppressed the SNAP-induced activation in a dose-dependent manner. Activation by a NO-donor is dependent on the influx of calcium from extracellular spaces, because the blockage of calcium channels by verapamil had significantly reduced the activation rate in SNAP-treated oocytes. The blockage of inositol triphosphate receptors had no effect on the activation of oocytes by a NO-donor. On the other hand, the blockers of ryanodine receptors, procaine and ruthenium red, inhibited the activation of oocytes induced by a NO-donor. These data indicate that the activation of pig oocytes by a NO-donor is calcium-dependent. The calcium for the activation is mobilized from extracellular and intracellular spaces. For the mobilization of intracellular calcium stores, it is the ryanodine receptors and not the inositol triphosphate receptors that play a key role.

Animals↗

PubMed2004

Both 3,4-dihydroxyphenylalanine and dopamine releases are regulated by Ca2+-induced Ca2+ releasing system in rat striatum.

To clarify the striatal Ca2+-dependent monoaminergic exocytosis mechanisms, this study determined the effects of the Ca2+-induced Ca2+ releasing system (CICR), containing inositol-trisphosphate-receptor (IP3R) and ryanodine-receptor (RyR), on striatal releases of dopamine and its precursor, 3,4-dihydroxyphenylalanine (DOPA), using microdialysis. The basal dopamine release is regulated by IP3R but not by RyR, whereas basal DOPA release does not require CICR. The K+-evoked releases of DOPA and dopamine were enhanced by IP3R agonist, whereas RyR agonist reduced it. Additionally, inhibition of dopamine release induced by RyR hyperactivation was prevented by inhibition of L-type voltage-sensitive Ca2+-channel activity. These present results suggest that CICR-associated regulation of striatal releases of DOPA and dopamine is restrictive during the resting stage, whereas CICRs play an important role as a reserve mechanism of exocytosis of striatal DOPA and dopamine during the hyperexcitable stage.

Adenosine↗

PubMed2005

Cannabinoids produce neuroprotection by reducing intracellular calcium release from ryanodine-sensitive stores.

Exogenously administered cannabinoids are neuroprotective in several different cellular and animal models. In the current study, two cannabinoid CB1 receptor ligands (WIN 55,212-2, CP 55,940) markedly reduced hippocampal cell death, in a time-dependent manner, in cultured neurons subjected to high levels of NMDA (15 microM). WIN 55,212-2 was also shown to inhibit the NMDA-induced increase in intracellular calcium concentration ([Ca2+](i)) indicated by FURA-2 fluorescence imaging in the same cultured neurons. Changes in [Ca2+](i) occurred with similar concentrations (25-100 nM) and in the same time-dependent manner (pre-exposure 1-15 min) as CB1 receptor mediated neuroprotective actions. Both effects were blocked by the CB1 receptor antagonist SR141716A. An underlying mechanism was indicated by the fact that (1) the NMDA-induced increase in [Ca2+](i) was inhibited by ryanodine, implicating a ryanodine receptor (RyR) coupled intracellular calcium channel, and (2) the cannabinoid influence involved a reduction in cAMP cAMP-dependent protein kinase (PKA) dependent phosphorylation of the same RyR levels that regulate channel. Moreover the time course of CB1 receptor mediated inhibition of PKA phosphorylation was directly related to effective pre-exposure intervals for cannabinoid neuroprotection. Control studies ruled out the involvement of inositol-trisphosphate (IP3) pathways, enhanced calcium reuptake and voltage sensitive calcium channels in the neuroprotective process. The results suggest that cannabinoids prevent cell death by initiating a time and dose dependent inhibition of adenylyl cyclase, that outlasts direct action at the CB1 receptor and is capable of reducing [Ca2+](i) via a cAMP/PKA-dependent process during the neurotoxic event.

Animals↗

PubMed2005

Biphasic actions of topiramate on monoamine exocytosis associated with both soluble N-ethylmaleimide-sensitive factor attachment protein receptors and Ca(2+)-induced Ca(2+)-releasing systems.

To explore the pharmacological mechanisms of topiramate (TPM), we determined the effects of TPM on monoamine (dopamine and serotonin) exocytosis associated with N-ethylmaleimide-sensitive factor attachment protein receptors and Ca(2+)-induced Ca(2+)-releasing systems, including inositol-triphosphate receptor and ryanodine receptor in freely moving rat pre-frontal cortex using in vivo microdialysis. During resting stage, Ca(2+) output from endoplasmic reticulum Ca(2+) store via inositol-triphosphate receptor regulates syntaxin-associated monoamine exocytosis mechanism, whereas during neuronal hyperexcitable stage, Ca(2+) output via ryanodine receptor regulates synaptobrevin-associated monoamine exocytosis mechanism. Basal monoamine releases were increased and decreased by therapeutically relevant and supratherapeutic concentration of TPM, respectively. The therapeutic-relevant concentration of TPM increased Ca(2+)-evoked release concentration-dependently; however, its stimulatory effect was attenuated in the supratherapeutic range. The K(+)-evoked releases were reduced by TPM concentration-dependently (from therapeutic to supratherapeutic ranges). The therapeutic-relevant concentration of TPM-induced elevation of basal release was reduced by cleavage with syntaxin and inhibition of inositol-triphosphate receptor predominantly, by cleavage with SNAP-25 and synaptobrevin weakly, but not by ryanodine receptor inhibitor. The therapeutic-relevant concentration of TPM-induced elevation of Ca(2+)-evoked release was reduced by cleavage with syntaxin and inositol-triphosphate receptor inhibitor selectively. The therapeutic-relevant concentration of TPM-induced reduction of K(+)-evoked monoamine release was abolished by cleavage with synaptobrevin, but was not affected by cleavage with SNAP-25 or synaptobrevin. The stimulatory effect of ryanodine receptor agonist on K(+)-evoked monoamine release was reduced by TPM, whereas that of inositol-triphosphate receptor agonist was not affected by TPM. Therefore, these results indicate that the combination of the effects of TPM on exocytosis mechanisms associated with SNARE and Ca(2+)-induced Ca(2+)-releasing systems, enhancement of inositol-triphosphate receptor/syntaxin and inhibition of ryanodine receptor/synaptobrevin in pre-frontal cortex, may be involved in clinical actions of TPM.

Animals↗

PubMed2004

EPR, IR and electronic spectral studies on Mn(II), Co(II), Ni(II) and Cu(II) complexes with a new 22-membered azamacrocyclic [N4] ligand.

The complexes of transition metal ions with an azamacrocyclic tetradentate nitrogen donor [N4] ligand viz. 2,6,12,16,21,22-hexaaza;3,5,13,15-tetramethyltricyclo[15.3.1.1(7-11)] docosa;1(21),2,5,7,9,11(22),12,15,17,19-decaene (L) have been synthesized. All the complexes were found to have general composition M(L)X2 [where M = manganese(II), cobalt(II), nickel(II) and copper(II) and X = Cl- & NO3-]. All the complexes are characterized by the elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, 1H NMR, IR, electronic, EPR spectral and cyclic voltammetric studies. An octahedral geometry was assigned for Mn(II), Co(II) and Ni(II) complexes and tetragonal for Cu(II) complexes. The biological actions of the ligand and complexes have been screened in vitro against many bacteria and pathogenic fungi to study their comparative capacity to inhibit the growth.

Anti-Bacterial Agents↗

PubMed2004

EPR and electronic spectral studies on Co(II), Ni(II) and Cu(II) complexes with a new tetradentate [N4] macrocyclic ligand and their biological activity.

Cobalt(II), nickel(II) and copper(II) complexes having the general composition M(L)X2 (where M = CO(II), Ni(II) and Cu(II), L = ligand, i.e. 3,4,12,13-tetraketo-2,5,11,14,19,20-hexaazatricyclo[13.3.1.1(6-10)]cosane; 1(19),6,8,10(20),15,17-hexaene and X stands for Cl-; NO3- and SO42-), have been prepared. The structure of the complexes has been elucidated by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, electronic and EPR spectral studies. The magnetic moment measurements of the complexes indicate that the metal ion is in high-spin state. On the basis of IR, electronic and EPR spectral studies an octahedral geometry was assigned for Co(II) and Ni(II) complexes whereas tetragonal geometry for Cu(II) complexes. This ligand and its complexes were also screened against bacteria and pathogenic fungi in vitro.

Anti-Bacterial Agents↗

PubMed2004

Spectroscopic, redox and biological activities of transition metal complexes with ons donor macrocyclic ligand derived from semicarbazide and thiodiglycolic acid.

A novel macrocyclic Schiff base ligand (2,5,9,12,14,18-hexaoxo-7,16-dithia-1,3,4,10,11,13-hexaazacycloocta-decane (H6L) with N4S2 coordinating sites was prepared by the reaction of the semicarbazide and thiodiglycolic acid. The transition metal complexes with macrocyclic ligand were synthesized and characterized by elemental analyses, magnetic susceptibility measurements, molar conductance, IR, electronic, and EPR spectral studies. Mass, 1H NMR and IR spectral techniques suggest the structural features of macrocyclic ligand. Magnetic and electronic spectral studies suggest an octahedral geometry of complexes. Electrochemical behaviour of cobalt, nickel and copper complexes were determined by cyclic voltammetry. The cyclic voltammogram of the copper complex at room temperature shows a quasi-reversible peaks for Cu(III)-->Cu(II) and Cu(II)-->Cu(I) couples. The macrocyclic ligand and its complexes show growth inhibitory activity against pathogenic bacteria and plant pathogenic fungi A. niger, A. alternata and P. variotii. Most of the complexes have higher activities than that of free ligand.

Anti-Bacterial Agents↗

PubMed2004

Spectroscopic studies on Mn(II), Co(II), Ni(II), and Cu(II) complexes with N-donor tetradentate (N4) macrocyclic ligand derived from ethylcinnamate moiety.

Manganese(II), cobalt(II), nickel(II), and copper(II) complexes are synthesized with a novel tetradentate ligand, viz. 1,5,9,13-tetraaza-6,14-dioxo-8,16-diphenylcyclohexadecane (L) and characterized by the elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, 1H NMR, IR, electronic, and EPR spectral studies. The molar conductance measurements of the complexes in DMSO correspond to be nonelectrolyte nature for Mn(II), Co(II), and Cu(II) whereas 1:2 electrolytes for Ni(II) complexes. Thus, these complexes may be formulated as [M(L)X(2)] and [Ni(L)]X(2), respectively (where M = Mn(II), Co(II), and Cu(II) and X = Cl- and NO(3-)). On the basis of IR, electronic, and EPR spectral studies an octahedral geometry has been assigned for Mn(II) and Co(II) complexes, square-planar for Ni(II) whereas tetragonal for Cu(II) complexes. The ligand and its complexes were also evaluated against the growth of bacteria and pathogenic fungi in vitro.

Cinnamates↗

PubMed2005

Electronic, cyclic voltammetry, IR and EPR spectral studies of copper(II) complexes with 12-membered N4, N2O2 and N2S2 donor macrocyclic ligands.

A new series of copper(II) complexes have been synthesized with macrocyclic ligands having three different donating atoms in the macrocyclic ring. It has been shown that the stereochemistry of complexes is dependent on the coordinated anions. These complexes are characterized by various physicochemical techniques, viz. elemental analysis, molar conductance, magnetic susceptibility measurements, IR, electronic, 1H NMR and EPR spectral studies. Cyclic voltammetric behavior of the complexes has also been discussed. The observed anisotropic g-values indicate that the chloro and acetato complexes are six-coordinate tetragonal. Whereas the sulfato and nitrato complexes are found to have five-coordinate square-pyramidal and four-coordinate square-planar geometry, respectively.

Acetates↗

PubMed2005

Pentacoordinated Cu(II)/Zn(II) complexes bearing macrocyclic skeleton: synthesis, spectroscopic and molecular structure optimization studies.

2,6-Diacetylpyridine and 1,2-diaminoethane in the presence of copper(II) and zinc(II) chlorides containing a few drops of acetic acid were condensed into compositions [CuLH2]2.2HCl.H2O (1), [Cu2LPyz]2.2HCl.4CH3COCH3 (2) [CuZnLPyz]2.2HCl.2CH3COCH3.10H2O (3) and [ZnL'Cl]3.3HCl.3H2O (4) substantiated by elemental analyses, IR, UV-vis, 1H NMR and FAB mass spectral data. Demetallation of a Ni(II) complex (isolated as above) afforded macrocyclic skeleton LH4, whereas L' symbolizes a skeleton of the ligand containing only ethylenediamine and 2,6-diacetylpyridine. Molecular structure optimization using MM2 force field calculations for the complexes revealed distorted square pyramidal geometry around Cu(II) centers in complexes 1 and 2 and tetrahedral geometry around Cu(II) and Zn(II) centers with different degrees of distortion in complex 3 whereas three Zn(II) atoms (each in distorted square pyramidal geometry) attached via Cl bridges form a cyclic structure in complex 4. In complexes 1 and 2,Cu-Cu = 2.63-2.66 angstroms indicated the possibility of coupling between the two Cu(II) centers which has been supported by lower magnetic moment as well as ESR spectra showing half-field signal.

Computer Simulation↗

PubMed2005

Magnetic, electronic and electrochemical studies of mono and binuclear Cu(II) complexes using novel macrocyclic ligands.

A series of new mono and binuclear copper (II) complexes [Cul]X(2)and [Cu(2)lX(2)] where 1 = L(1), L(2) and L(3) are the macrocyclic ligands. In mononuclear complexes the geometry of Cu(II) ion is distorted squareplanar and in binuclear complexes the geometry of Cu(II) is tetragonal. The synthesized complexes were characterized by spectroscopic (IR,UV-vis and ESR) techniques. Electrochemical studies of the complexes reveals that all the mononuclear Cu(II) complexes show a single quasireversible one-electron transfer reduction wave (E(pc) = -0.76 to -0.84V) and the binuclear complexes show two quasireversible one electron transfer reduction waves (E(pc)(1) = -0.86 to -1.01V, E(pc)(2) = -1.11 to -1.43V) in cathodic region. The ESR spectra of mononuclear complexes show four lines with nuclear hyperfine splittings with the observed g(11) values in the ranges 2.20-2.28, g( perpendicular) = 2.01-2.06 and A(11) = 125-273. The binuclear complexes show a broad ESR spectra with g = 2.10-2.11. The room temperature magnetic moment values for the mononuclear complexes are in the range [mu(eff) = 1.70-1.72BM] and for the binuclear complexes the range is [mu(eff) = 1.46-1.59BM].

Catechols↗

PubMed2004

The use of IR, magnetism, reflectance, and mass spectra together with thermal analyses in structure investigation of codeine phosphate complexes of d-block elements.

Codeine is an analgesic with uses similar to morphines, but it is of much less effect, i.e., it had a mild sedative effect; codeine is usually used as the phosphate form (Cod.P) and is often administrated by mouth with aspirin of paracetamol. Due to its serious use, if it is in large dose, attention is paid in this research to the synthesis and stereochemistry of new iron, cobalt, nickel, copper, and zinc complexes of this drug in both solution and the solid states. The spectra of these complexes in solution and the study of their stoichiometry refer to the formation of 1:1 ratio of metal (M) to ligand (L). The steriochemical structures of the solid complexes were studied on the basis of their analytical, spectroscopic, magnetic, and thermal data. Infrared spectra proved the presence of MO bonds. Magnetic susceptibility and solid reflectance spectral measurements were used to infer the structures. The prepared complexes were found to have the general formulae [ML(OH)(x)(H2O)(y)](H2O)(z)H3PO4, M: Co(II), Ni(II), and Cu(II), x = 1, y = 0, z = 0; M: Fe(II), x = 1, y = 2, z = 1; Fe(III), x = 2, y = 1, z = 0; Co(III), x = 0, y = 2, z = 1; Zn(II), x = 1, y = 0, z = 3; and L: (Cod.P) of the general formula C18H24NO7P (anhydrate). Octahedral, tetrahedral, and square planer structures were proposed for these complexes depending upon the magnetic and reflectance data and were confirmed by detailed mass and thermal analyses comparative studies.

Cations↗

PubMed2005

Mass, EPR, IR and electronic spectroscopic studies on newly synthesized macrocyclic ligand and its transition metal complexes.

Manganese(II), cobalt(II), nickel(II) and copper(II) complexes have been synthesized with a new tetradentate ligand viz. 1,3,7,9-tetraaza-2,4,8,10-tetraketo-6,12-diphenyl-cyclododecane (L) and characterized by the elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, 1H NMR, IR, electronic and EPR spectral studies. The molar conductance measurements of the complexes in DMF correspond to be nonelectrolytic nature for Mn(II), Co(II) and Cu(II) while 1:2 electrolytes for Ni(II) complexes. Thus, these complexes may be formulated as [M(L)X2] and [Ni(L)]X2 (where M=Mn(II), Co(II) and Cu(II) and X=Cl- and NO3-). On the basis of IR, electronic and EPR spectral studies an octahedral geometry has been assigned for Mn(II) and Co(II) complexes, square-planar for Ni(II) whereas tetragonal for Cu(II) complexes. The ligand and its complexes were also evaluated against the growth of bacteria and pathogenic fungi in vitro.

Anti-Infective Agents↗

PubMed2005

Spectral studies, cyclic voltammetry and synthesis of cobalt(II) and ruthenium(III) complexes with symmetric and asymmetric ring containing membered N2S2, N4, and N5 donor macrocyclic ligands.

Reaction of divalent cobalt(II) and trivalent ruthenium(III) salts (NO3, SCN and SO4) with macrocyclic ligands L1, L2 and L3 having N2S2, N4 and N5 core, have been designed and carry out. All these three macrocyclic ligands and their complexes were obtained in pure form. Their structures were investigated by using microanalytical analyses, IR, mass, magnetic moments, electronic and EPR spectral studies. The redox properties of the complexes were also examined by cyclic voltammetry. An interesting feature of complexes is that the relatively large rings of macrocyclic ligands prevent the macrocyclic rings from approaching the metal center as closely as they would, if they were not constrained. So the Ru-N distances are longer than expected due to ring size. Electrochemical studies show that the macrocyclic ligand L1 is more effective electron donors to ruthenium than of L2 and L3. Electronic spectral properties also show that the sulphur donor atom of L1 weakens the ligand field with respect to ligand-to-metal charge-transfer band. However it is expected that second-row transition metal-ligand bonds tend to be weaker than third-row transition metal-ligand bonds. There are well-established examples of reactions in which decreased of reactivity down a triad of transition metals is not observed. These novelties are usually attributed to pi-bonding effects for ligands such as carbon monoxide, solvent effects, or a change in mechanism.

Cobalt↗

PubMed2005

Electronic, EPR, magnetic and mass spectral studies of mono and homo-binuclear Co(II) and Cu(II) complexes with a novel macrocyclic ligand.

A series of 20-memebered macro-cyclic metal(II) complexes have been synthesized by a macro-cyclic ligand, i.e. 1,5,11,15-tetraaza-6,10,16,20-tetraoxo-8,18-dithia-cyclocosane, it was prepared by the condensation reaction of 1,3-diaminopropane with thiodiglycolic acid. The bonding and stereochemistry of the complexes have been characterized by elemental analysis, magnetic moment, molar conductance, mass, 1H NMR, IR, electronic and EPR spectral studies. The mononuclear complexes of the type [ML]X2 have been found to have distorted octahedral geometry and the binuclear complexes [M2LX2]X2 were found to possess square planar configuration around the central metal ion.

Anions↗

PubMed2005

Synthesis, characterization and semi-empirical calculations for the thiocyanate linkage isomers of an (alpha-iminooxime)cobalt(III) macrocyclic complex.

Herein we report the synthetic route and detailed characterization of the macrocyclic complex [Co(dohpn)(SCN)2] and its linkage isomer (dohpn=2,3,9,10-tetramethyl-1,4,8,11-tetraazaundecane-1,3,8,10-tetraen-11-ol-1-olate and py=pyridine) based on analytical, spectroscopic and electrochemical methods. Structural, vibrational and electronic features are discussed and a coherent assignment is proposed on the basis of semi-empirical theoretical calculations.

Cobalt↗