Synthesis and metal ion complexation of acyclic Schiff base podands with lipophilic amide and ester end groups

A series of acyclic Schiff base podands 14?C19 with lipophilic amide and ester end groups were synthesized in good yield and in a simple way. Their transition metal ions complexation was studied using conductometric method in acetonitrile (AN) at 25 °C. Schiff base podands 14?C16 showed a continuous decrease in the molar conductances in their complexation with Hg²⁺, Pb²⁺, Cu²⁺, Zn²⁺ and Cd²⁺ which begins to level off at a mole ratio of 1:1 crown-to-metal indicating the formation of a stable 1:1 complexes. The order of the stability constants of the metal ions studied with the Schiff base podands 14, 15 and 16 is: Hg²⁺ > Pb²⁺ > Cu²⁺ > Zn²⁺ > Cd²⁺ > Ag⁺. Metal ion complexation by acyclic diamide or diester podands involves presumably the oxygen atoms of the carbonyl groups in addition to the nitrogen atoms of the imino groups.     

Schwingungsspektroskopische Untersuchung der Wechselwirkung von Metallkationen mit Dimethylformamid

The interaction of a series of cations with dimethylformamide is investigated using IR spectroscopy. The complexation of a cation by the amide is shown to weaken the C=O bond and to enforce both C–N and C–H bonds of the ligand. These results are in agreement withCNDO/2 calculations on force constants and vibration frequencies. The IR results, which can reflect only qualitative trends concerning the changes of the bonding situation in the ligand molecule upon metal ion complexation, are compared with the more accurate data obtained in recent NMR line shape investigations.     

Synthesis of 2,6—（substituded）pyridine Derivatives Using Amide and Imine Groups

A new ‘two-armed’ acyclic diamide Ia 2,6-bis(1-ethanecarbozamido-2-amino)pyridine,and a new series of aromatic aldehyde schiff bases containing pyridine ring and arnide bridge,ILa-f, were prepared.The compounds were characterized by elemental analysis,IR,^1HNMR and MS.The bioactivity half inhibitory concentration C1/2 is given.     

In situ electrochemical complex formation for selected metal ions based on controlled release of the pyrrolidine dithiocarbamate ligand from polypyrrole polymer

A novel in situ electrochemical complex formation for selected metal ions has been developed. The scheme involves the use of polymeric material as a conducting agent into which the complexing agent pyrrolidine dithiocarbamate ligand is incorporated. The property of the polymer enables electrochemically controlled release of the reagent into a flowing solution. A dual-electrode arrangement in a thin layer transducer, the series dual-electrode detector, is used to release the ligand and detect it or its metal complex. The influence of the film prepared for ligand incorporation and the ion exchange process after polymer synthesis was studied. The film thickness for ligand incorporation and the negative potential required to trigger the ligand release were investigated. Finally, in flow injection analysis (FIA), the effects of the ionic strength of the supporting electrolyte and the flow rate on reagent release behavior and metal ion complexation were examined.     

Artificial peptidase with an active site comprising a Cu(II) center and a proximal guanidinium ion. A carboxypeptidase A analogue

An immobile artificial metallopeptidase having a well-defined active site was constructed on the backbone of cross-linked polystyrene by adjoining a guanidinium moiety to the Cu(II) complex of a tetraaza ligand. The catalyst (CABP) and intermediate polymers were characterized by elemental analysis, IR, inductively coupled plasma measurement, electron probe microanalysis, test for primary amines, binding of Cu(II) ion, and complexation of p-nitrobenzoate ion. CABP effectively catalyzed amide hydrolysis of carboxyl-containing N-acyl amino acids. The catalytic rate of CABP in the hydrolysis of unactivated amides was comparable to that of the catalytic antibody with the highest peptidase activity reported to date. It is proposed that the guanidinium moiety of CABP recognizes the carboxylate anion of the substrate whereas the Cu(II) center participates in the cleavage of the amide bond of the complexed substrate. Several characteristic features of carboxypeptidase A were reproduced by CABP: catalytic action of the metal ion, participation of guanidinium in substrate recognition, hydrolysis of small unactivated amides, and substrate selectivity toward amide bonds adjacent to a carboxylate group.     

Investigation of Metal Ion Complexation of π-Coordinate Calixarene Derivatives by Electrospray-Ionization Mass Spectrometry

Complexation of π-coordinate calix[4]arene derivatives toward soft metal ions, silver and thallium (I) ions, has been studied by electrospray-ionization mass spectrometry. Competitive metal–ion complexation of three calix[4]arene derivatives demonstrates a significant effect of olefinic substituents and its location on the silver ion complexation, but there was no effect of them on the thallium ion complexation. The stability constants for the metal ion complexes of the calixarene derivatives in methanol have been successfully determined by a mass-spectrometric method using 18-crown-6 as the reference ligand.     

The preparation and properties of neutral diamide ionophores for group IIa metal cations

The preparation of a series of neutral ligands featuring ether and N-methyl-N-carbethoxypentylamide groups is described. These ligands as well as related ones bearing other diamide groups are shown to selectively chelate Group IIA cations by picrate extraction from water to methylene chloride. The changes in UV absorption of aromatic rings and amide groups in the ligands upon titration with metal salts in methanol allow the estimation of the stoichiometry of complexation and the ordering of cation binding. The observed selectivity sequences of cation extraction and binding are briefly discussed. Preliminary proton and ¹³C NMR studies on the effect of addition of Group IIA cation salts to several of the ligands in methanol suggest that most of the complexation occurs at the central ether and amide groups. ¹³C NMR T₁ changes by the Inversion Recovery Fourier Transform method are in agreement with the cation-induced shift data.     

Separation of metal ions and metal-containing species by micellar electrokinetic capillary chromatography, including utilisation of metal ions in separations of other species

The use of micellar electrokinetic capillary chromatography (MEKC) for the separation of metal ions and metal-containing species is reviewed, together with the use of metal ions as a means to separate other species. Topics covered include the manipulation of separation selectivity through the use of complexation reactions induced by addition of a metal ion to the background electrolyte, enantiomeric separations facilitated through metal-analyte interactions, separation of organometallic species, separation of stable metal complexes in which the entire complex is the analyte and the separation of metal ions as analytes using pre-capillary or on-capillary complexation reactions with a suitable ligand.     

Synthesis of a tetrahomodioxacalix[4]arene tetraamide and the crystal structure of its lead ion complex

The 1,4-alternate tetrahomodioxacalix[4]arene tetraamide 4 with four p-phenyl groups on its upper rim was synthesized. In two-phase metal picrate extraction, 4 exhibited Pb2+ selectivity with formation of a 1:1 complex in chloroform. In the solid-state structure of the 4*Pb(Pic)2 complex, Pb2+ is bound by the carbonyl oxygens of two adjacent amide groups and an aryl-alkyl ether oxygen atom of one of these amide-containing substituents. The crystal structure and 1H NMR spectrum of the 4*Pb2+ complex reveals pi-metal ion complexation of one aromatic ring in the ligand with Pb2+.     

N,N'-Bis(3-triethoxysilyl)phthalic Diamide, N,N'-Bis(3-triethoxysilyl)malonic Damide and Derivatives

Condensation of 3-triethoxysilylpropylamine with malonic amide was studied. The condensation products, dicarboxylic acid diamides (malonic and phthalic), were used for peretherification with triethanolamine and thus new representatives of silatran series compounds were prepared: N,N'-bis(3-triethoxysilyl)malonic diamide and -phthalic diamide. By hydrolytic polycondensation of N,N'-bis(3-triethoxysilyl)malonic diamide we synthesized an organosilicon polymer with silsesquioxane structure, which we studied as a sorbent of platinum group metals rhodium, palladium and platinum. Peculiar features of sorption activity of the polymer and speculative mechanism of metal sorption are discussed.     

Cationic lanthanide complexes of neutral tripodal N,O ligands: enthalpy versus entropy-driven podate formation in water

The cationic lanthanide complexes of two neutral tripodal N,O ligands, tpa (tris[(2-pyridyl)methyl]amine) and tpaam (tris[6-((2-N,N-diethylcarbamoyl)pyridyl)methyl]amine) are studied in water. The analysis of the proton lanthanide induced NMR shifts indicate that there is no abrupt structural change in the middle of the rare-earth series. Unexpectedly, the formation constant values of the lanthanide podates of tpaam and tpa in D2O at 298 K are similar, suggesting that the addition of the three amide groups to the ligand tpa does not lead to any increase in stability of the lanthanide complexes of tpaam in respect to tpa, even though the amide groups are coordinated to the metal in aqueous solution. The measurement of the enthalpy and entropy changes of the complexation reactions shows that the two similar ligands tpa and tpaam have different driving forces for lanthanide complexation. Indeed, the formation of tpa podates benefits from an exothermic enthalpy change associated with a small entropy change, whereas the complexation reaction with tpaam is clearly entropy-driven though opposed by a positive enthalpy change. The hydration states of the europium complexes were measured by luminescence and show the coordination of 4-5 water ligands in [Eu(tpa)]3+ whereas there are only 2 in [Eu(tpaam)]3+. Therefore the heptadentate ligand tpaam releases the translational entropy of more water molecules than does the tetradentate ligand tpa.     

Kinetic studies of complexation reactions of water-soluble hydrazones with nickel(II) and palladium(II) ions

The kinetics of complexation reactions of five water-soluble heterocyclic hydrazones with nickel(II) and palladium(II) ions have been investigated by stopped-flow spectrophotometry. Rates of complexations with nickel(II) and palladium(II) in the absence of chloride ion were found to be proportional to the first order of the ligand and metal ion concentrations and to the inverse first order of the hydrogen ion concentration except for the complexation of alpha-(2-benzimidazolyl)-alpha-(5-nitro-2-pyridyl)hydrazono-3-toluenesulfonic acid with palladium(II). Rates of complexation with palladium(II) in the presence of chloride ion were best described by a two-term expression, both terms being first order in the palladium ion and ligand concentrations and inverse first order in the hydrogen ion concentration. The first term has zero dependence of the chloride ion concentration, whereas the second is first order with respect to the chloride ion concentration. The rate constant for each complexation reaction was determined. The complexation of the hydrazones with nickel(II) was estimated to go according to an Eigen mechanism and that with palladium (II) according to the associative mechanism.     

Evaluation of metal complexation as an alternative to protonation for electrospray ionization of pharmaceutical compounds

The use of pyridyl and polyether compounds as auxiliary ligands to promote metal complexation of a series of pharmaceutical analytes by electrospray ionization (ESI) is explored as an alternative to conventional protonation by ESI. The auxiliary ligands vary in the number and nature of binding sites, the orientation of the binding sites with respect to each other, and the conformational flexibility of the ligand during complexation of the metal ion. The ESI of ternary solutions composed of a pharmaceutical substrate, a transition metal ion salt, and an auxiliary complexation agent generate metal complexes of the type [(L-H⁺)M^II(aux)]⁺, where L is the pharmaceutical, M is either copper, nickel, or cobalt, and aux is the auxiliary ligand. Overall, the pyridine-type ligands are more useful for the generation of ternary metal complexes than the polyether-type ligands, which preferentially complex sodium ions and, upon collisional activation, undergo fragmentation of the polyether skeleton in addition to the structurally informative dissociation of the analytes. The auxiliary ligand that exhibits the best performance is 2,2′-dipyridine; its ternary metal complexes enhance the structural characterization of five of the pharmaceuticals by promoting a greater number of fragments relative to the CAD patterns of the protonated substrates.     

Dissociation of polyether-transition metal ion dimer complexes in a quadrupole ion trap

The formation and dissociation of dimer complexes consisting of a transition metal ion and two polyether ligands is examined in a quadrupole ion trap mass spectrometer. Reactions of three transition metals (Ni, Cu, Co) with three crown ethers and four acyclic ethers (glymes) are studied. Singly charged species are created from ion-molecule reactions between laser-desorbed monopositive metal ions and the neutral polyethers. Doubly charged complexes are generated from electrospray ionization of solutions containing metal salts and polyethers. For the singly charged complexes, the capability for dimer formation by the ethers is dependent on the number of available coordination sites on the ligand and its ability to fully coordinate the metal ion. For example, 18-crown-6 never forms dimer complexes, but 12-crown-4 readily forms dimers. For the more flexible acyclic ethers, the ligands that have four or more oxygen atoms do not form dimer complexes because the acyclic ligands have sufficient flexibility to wrap around the metal ion and prevent attachment of a second ligand. For the doubly charged complexes, dimers are observed for all of the crown ethers and glymes, thus showing no dependence on the flexibility or number of coordination sites of the polyether. The nonselectivity of dimer formation is attributed to the higher charge density of the doubly charged metal center, resulting in stronger coordination abilities. Collisionally activated dissociation is used to evaluate the structures of the metal-polyether dimer complexes. Radical fragmentation processes are observed for some of the singly charged dimer complexes because these pathways allow the monopositive metal ion to attain a more favorable 2 + oxidation state. These radical losses are observed for the dimer complexes but not for the monomer complexes because the dimer structures have two independent ligands, a feature that enhances the coordination geometry of the complex and allows more flexibility for the rearrangements necessary for loss of radical species. Dissociation of the doubly charged complexes generated by electrospray ionization does not result in losses of radical neutrals because the metal ions already exist in favorable 2+ oxidation states.     

Potentiometric Selectivities of Dibenzo-16-crown-5 Compounds for Alkali and Alkaline Earth Metal Cations and Ammonium Ions

Potentiometric selectivities toward alkali and alkaline earth metal cations and ammonium ions are utilized to probe the complexation of these cationic species by dibenzo-16-crown-5 lariat ethers. Attachment of one or two pendant groups to the central carbon of the three-carbon bridge in dibenzo-16-crown-5 markedly alters the potentiometric responses of the ionophores when incorporated in solvent polymeric membrane electrodes. Results obtained for dibenzo-16-crown-5 compounds with coordinating side arms containing ether, carboxylic acid, ester, and amide groups provide insight into the role of the side arm in metal ion complexation by lariat ether compounds.     

Structural aspects of metal–amide complexes

An exhaustive survey of crystal structure data on simple amides and metal complexes containing monodentate amide ligands has been performed. Statistical analysis of structural features are reported as a function of the degree of alkylation of the amide functional group, the type of metal ion in the amide complex, and the type of binding to the metal ion. Average values are reported for bond lengths, bond angles, and torsional angles. Orientational preferences of the coordinated amide ligand are discussed in terms of M–O–C bond angles and M–O–C–N torsion angles.     

Recognition, encapsulation, and selective fluorescence sensing of nitrate anion by neutral C3-symmetric tripodal podands bearing amide functionality

A series of neutral C(3)-symmetric acyclic artificial receptors incorporating amide functionality has been designed, synthesized, and fully characterized. Upon protonation, these conformationally flexible N-bridged tripodal podands 1-5 form in situ cone shape conformation through hydrogen bonding and C-H···π interactions. The protonation-induced interior preorganized cavity is capable of entrapping nitrate anions through the amide N-H bonds to form discrete nitrate complexes (1a-5a), which were fully characterized by NMR, HRESI mass spectra, and single crystal structures. By incorporating suitable fluorophores at each branch of the tripod receptor, the resulting fluorescent receptor 5 selectively recognized nitrate anions by fluorescent quenching in a DMSO solution and displayed one of the highest binding affinities for nitrate anions reported so far in polar media. Receptor 5 represents a unique example of a neutral receptor for the recognition of nitrate anions in polar solvent media by its zwitterionic form. The possible mechanism of proton-induced preorganization of these flexible, acyclic receptors in a convergent cone conformation followed by nitrate complexation has been proposed to rationalize the effective nitrate recognition.     

Complexation ion chromatography —an overview of developments and trends in trace metal analysis

Complexation ion chromatography (IC), including all ion chromatographic modes in which complexation is exploited for the separation and detection of metal ions in different ways, is now a widely accepted method of trace metal analysis. Some of the significant advances in the theoretical aspects and practical applications of complexation IC modifications (non-suppressed cation chromatography with complex- forming mobile phases, coordination chromatography with chelate-forming bonded phases, ion-exchange and ion-pair chromatography of anionic metal chelates) recently developed in the authors' laboratories are reviewed. The retention behaviour and separation mechanism of non-complexed and completed metal analytes are discussed from the point of view of basic coordination chemistry (stability of metal complexes, effective charge of metal atom, ligand completing ability, etc.). Comparisons and contrasts between various metal complexation IC techniques and their common features and advantages relative to other methods used in analyses for transition and heavy metal ions are evaluated.     

Ligand-exchange chemistry of Cr13-polyacrylamide gels

Evidence that ligand-induced de-gelation of Cr(+3)/polyacrylamide (PAAm) gels involves simple extraction of Cr(+3) from the gel matrix has been obtained from rheological studies. Kinetic experiments provide evidence that de-gelation involves dissociative ligand exchange at Cr(+3). On the basis of de-gelation results acetate is suggested to be a poor thermodynamic model for the bonding of PAAm to Cr(+3) and it is hypothesized that Cr(+3)/PAAm complexation may involve bonding to both a polymer carboxylate and a neighboring amide group.     

Structural Criteria for the Rational Design of Selective Ligands. 2. Effect of Alkyl Substitution on Metal Ion Complex Stability with Ligands Bearing Ethylene-Bridged Ether Donors

A novel approach is presented for the application and interpretation of molecular mechanics calculations in ligand structural design. The methodology yields strain energies that (i) provide a yardstick for the measurement of ligand binding site organization for metal ion complexation and (ii) allow the comparison of any two ligands independent of either the number and type of donor atoms or the identity of the metal ion. Application of this methodology is demonstrated in a detailed examination of the influence of alkyl substitution on the structural organization of ethylene-bridged, bidentate, ether donor ligands for the alkali and alkaline earth cations. Nine cases are examined, including the unsubstituted ethylene bridge (dimethoxyethane), all possible arrangements of individual alkyl groups (monoalkylation, gem-dialkylation, meso-dialkylation,d,l-dialkylation, trialkylation, and tetraalkylation), and both cis and trans attachments of the cyclohexyl group. The calculated degree of binding site organization for metal ion complexation afforded by these connecting structures is shown to correlate with known changes in complex stability caused by alkyl substitution of crown ether macrocycles.