New chromogens of the ferroin-type--II. Pyrido and pyridyl derivatives of phenazine and quinoxaline

Eleven pyrido and pyridyl derivatives of phenazine (6) and quinoxaline (5) have been examined as chromogens of the ferroin type for iron(II) and copper(I). Three of the quinoxaline derivatives show promise as reagents for iron(II) but are expensive and difficult to prepare.     

New chromogens of the ferroin type-V Pyridylpyrimidines, bidiazines and other substituted derivatives of diazines

Spectrophotometric studies of the reactions of iron(II), copper(I) and cobalt(II) with 33 new compounds have demonstrated that the chromogenic properties of diazyl groups are inferior to those of triazyl or pyridyl groups when incorporated into the ferroin chromophore group. The metal complexes of the diazyl derivatives are less stable than those of the corresponding pyridyl and triazyl derivatives. Conditional formation constants of the iron(II) chelates of some representative diazyl derivatives indicate that pyridazyl groups impart greater stabilities than pyrimidyl or pyrazyl groups. Five of the new chromogens have structures that suggest they can chelate iron(II) without steric hindrance, either as bidentate or as terdenate ligands. Although the terdentate mode would ordinarily be expected, two of the five were found to act preferably as bidentate ligands.     

A novel ferroin membrane sensor for potentiometric determination of iron

A novel potentiometric approach for both batch and flow injection determination of iron(II) and/or iron(III) is described. It is based on the formation and monitoring of ferroin with a PVC membrane sensor containing ferroin-TPB as an electroactive component plasticized with 2-nitrophenyl phenyl ether. The sensor exhibits fast Nernstian response for ferroin with a cationic calibration slope of 30 +/- 0.2 mV/concentration decade down to 4 x 10(-7)M ferroin (0.03 ppm Fe) at pH 3-9. Interferences from common inorganic cations are negligible or can be eliminated by a pretreatment with DDC. The ferroin sensor was successfully applied to the determination of iron contents in water, alloys, rocks and pharmaceuticals. The results show good correlation with data obtained by the standard spectrophotometric ferroin method, the coefficient of correlation is better than 0.7%.     

A comparison of some pyridyl-substituted pyrazines as analytical reagents

A comparative study of six 2-pyridyl and 2-(6-methyl-pyridyl) derivatives of pyrazine as chromogenic reagents of the ferroin and cuproin types has established 2,3,5,6-tetrakis(2'-pyridyl)pyrazine as a highly sensitive reagent for iron(II); 2,3-bis(2'-pyridyl)-5,6-dihydropyrazine and 2,3-bis[2'-(6'-methyl pyridyl)]-5,6-dihydropyazine both show high sensitivity and characteristic high selectivity in their reactions with iron(II) and copper(I) respectively-the reaction with copper(I) being almost as sensitive as that given by bathocuproine. The ease with which the highly coloured metal chelates can be extracted into immiscible solvents to give stable solutions makes these reagents useful for the determination of traces of iron and copper.     

Some new chromogens for iron, cobalt, and copper Substituted hydrazidines and 1,2,4-triazines containing the ferroin group

The spectral characteristics and solution conditions requisite for formation of the iron(II), cobalt(II), and copper(I) complexes of some newly synthesised compounds containing the ferroin functional grouping have been determined. These properties are useful for evaluation of the possible analytical effectiveness of the compounds as spectrophotometric reagents for the determination of iron, cobalt, and copper.     

New chromogens of the ferroin type-VIII Some di- and trisubstituted 1,2,4-triazines, 3-substituted-9H-indeno[1,2-e]-1,2,4-triazin-9-ones, and di- and trisubstituted 1,2,4-triazolines

Thirty-six new ferroin compounds have been investigated as possible chelation regents for the calorimetric detection and determination of trace amounts of iron(II), copper(I), and cobalt(II). Spectral data, solution conditions favourable for chelate formation, and other data are reported. The results reveal that incorporation of triazoline heterocycles in ferroin chromophore groupings generally leads to poor chromogenic properties, except with respect to cobalt. Triazine groups, however, can give rise to superior properties. The most sensitive iron(II) chromogen of the ferroin type found to date and a promising new cobalt chromogen are described.     

New chromogens of the ferroin type-VII Some 3-substituted-1,2,4-triazines, 3,5-disubstituted-1,2,4-triazolines and triazoles, and 2,4- and 2,6-bis triazinyl and triazolinyl substituted pyridines

Chelation and chromogenic properties of 39 new ferroin compounds in reactions with iron(II), copper(I), and cobalt(II) have been investigated spectrophotometrically. The results demonstrate that the chromogenic properties of triazole and triazoline heterocycles are inferior to triazine and pyridine when incorporated into the ferroin chromophore grouping. The triazole and triazoline compounds also undergo hydrolytic decomposition, strongly catalysed by iron(II), making them unsuitable as colorimetric reagents. An outstanding chromogen was found from among the triazine derivatives which is superior in sensitivity to all ferroin-type chromogens previously studied.     

New chromogens of the ferroin-type-IV Oximes of substituted methyl and phenyl 2-pyridyl ketones

The spectral characteristics, and solution conditions requisite for formation, of the iron(II), cobalt(II), and copper(I) chelates of some newly synthesized oximes containing the ferroin functional grouping have been determined. For some of the oximes, both syn- and anti-isomers were available for study. NMR spectra of the isomers differed, enabling structural distinctions to be made. None of the anti-isomers formed coloured metal chelates. A practical method for distinguishing between the isomers can be based on these findings. Two of the compounds proved very promising as highly sensitive chromogens for determining iron in strongly alkaline materials.     

Sequential titration of iron(II) and vanadium(IV) mixtures with cerium(IV) sulphate, with ferroins as indicators

The titration of vanadium(IV) with cerium(IV) sulphate, with nitroferroin as indicator, is proposed. Unlike ferroin, the indicator does not need a catalyst in this system. By suitable choice of experimental conditions iron(II) can be titrated first to a ferroin end-point and then vanadium(IV) to a nitroferroin end-point.     

Synthesis of certain pyridinyl and diazinyl hydrazones containing one or more ferroin groups, and their chromogenic reactions with iron, copper, cobalt and nickel

Fifteen new hydrazones with one or more ferroin groups were prepared, and their chelation and chromogenic properties with iron(II), copper(I), cobalt(II) and nickel(II) were investigated. Improved sensitivity in the spectrophotometric determination of cobalt, copper, and nickel is provided by several of the new compounds. Several others are capable of forming unusually stable and interesting binuclear iron(II) complexes.     

New iron bis(imino)pyridyl complexes containing dendritic wedges for alkene oligomerisation

The synthesis, characterisation and catalytic behaviour of new iron bis(imino)pyridyl complexes containing dendritic wedges, as well as the synthesis of bis(para-hydroxyphenylimino)pyridines is described. The hydroxyl functionality of the bis(para-hydroxyphenylimino)pyridines was used to attach dendritic wedges of the carbosilane type as well as the benzylphenyl ether type. After attachment of the dendritic wedges, complexation of these ligands to iron(II) chloride was achieved. The resulting dendritically functionalised bis(imino)pyridyl iron complexes were tested in the catalytic oligomerisation of ethene.     

A New Simple and Sensitive Spectrophotometric Procedure for Determination of Adrenaline

Abstract

A new spectrophotometric procedure is described for the determination of ppm concentrations of adrenaline. The procedure is based on formation of Tris(O-phenanthroline)iron(II) complex (ferroin) upon reaction of adrenaline with an iron(III)-O-phenanthroline mixture in slightly acidic medium. The ferroin complex is then spectrophotometrically measured at 510 nm. In addition to being facile and rapid, the procedure is sufficiently selective and accurate, being particularly suitable for the assay of adrenaline in pharmaceutical formulations; the standard deviation didnot exceed 0.64%.     

Synthesis and metallochromic properties of some new mono- and bishydrazones of benzil and 2,2'-pyridil

Preparation of some new mono- and bishydrazones which possess the ferroin chromophoric group is described, together with results of spectrophotometric studies of their chelation reactions with iron(II), copper(I), cobalt(II), nickel(II) and zinc(II). Several of the new compounds show promise as chromogenic reagents for these metals. The results are also of interest with regard to structure-reaction relationships.     

Potentiometric determination of NTA, EDTA and DTPA in mixtures

Consecutive potentiometric determination of EDTA and NTA or DTPA and NTA is described. The method is based on the titration with iron(III) chloride at pH 4-5 in the presence of a small amount of ferroin and 1,10-phenanthroline which keeps the concentration of free iron(II) ions constant, thus making the potential dependent only on the free iron(III) concentration.     

Chemical oscillations in the metal ion-catalyzed bromate-4-aminophenol reaction

Temporal oscillations of the bromate-4-aminophenol system have been studied in the presence of four different catalysts:tris(1,10-phenanthroline)iron(II) sulfate(ferroin),Ce(III),Mn(II),and Fe(II).Transient temporal oscillations were observed in the four catalyzed systems when the reactions were conducted in a stirred batch reactor.The induction time was prolonged by the presence of ferroin,but it was shortened in the Ce(III)-and Mn(II)-catalyzed systems.On the other hand,the number of peaks was significantly decreased in the presence of ferroin.The development of oscillatory behaviour was found to be more sensitive to the ratio of bromate and 4-aminophenol concentration than to their absolute concentrations.The reaction rates of 4-aminophenol with Ce(IV) and 4-aminophenol with ferritin were measured directly by spectroscopic methods in a sulfuric acid medium.     

New chromogens of the ferroin type-X synthesis and chelation properties of some 2-thiazolyl- and 2-pyrimidinylhydrazones

Preparation of some new hydrazones which possess the ferroin chromophoric group is described, together with results of spectrophotometric studies of their chelation reactions with iron(II), copper(I), cobalt(II) and nickel(II). Several of the new compounds show promise as highly sensitive chromogenic reagents for simultaneous determinations of these metals.     

New chromogens of the ferroin-type-I. Substituted triazines related to 6-cyano-2,2'-bipyridine

A spectrophotometric study has been made of the iron(II), cobalt(II), nickel(II) and copper(I) chelates of seven new compounds that contain the ferroin functional grouping. None of the new compounds proved to be superior to chromogenic reagents currently in use, but the results are of interest in designing new chromogens.     

New chromogens of the ferroin type--III: some 2-substituted benzimidazole derivatives

A spectrophotometric study has been made of the iron(II) and copper(I) chelates of 23 new compounds that contain the ferroin functional grouping. Although none of the compounds proved to be superior to chromogenic reagents currently in use, the results are of interest from the point of view of designing new chromogens for iron and copper.     

Titrimetric determination of vanadium(IV) with cerium (IV)sulphate at room temperature using ferroin as indicator

A procedure has been developed for the visual titrimetric determination of vanadium(IV) with cerium(IV) sulphate, using ferroin is redox indicator. The method has been extended to the determination of iron(II) and vanadium(IV) in mixtures.     

Sequential titration of iron(II), antimony(III) and arsenic(III) in binary or ternary mixture

A simple titrimetric procedure for the determination of iron(II), antimony(III) and arsenic-(III) in a mixture, with cerium(IV) sulphate as titrant, is proposed. The end-points can all be detected with ferroin or potentiometrically. Phosphoric acid medium is used for titration of the iron(II), then acetic acid medium for the titration of antimony(III), and finally the arsenic(III) is titrated in presence of iodine as catalyst. The procedure utilizes a single portion of test solution; it can be adopted for the analysis of binary mixtures.