Showing papers in "Synthesis and Reactivity in Inorganic and Metal-organic Chemistry in 1985"

Synthesis of 1,3-Diphenyl-4,5-bis(hydroxyimino)imidazolidine and Its Complexes with Nickel(II), Cobalt(II), Copper(II), Palladium(II), and Uranyl(VI)

Abstract: 1, 3-Dipheny1-4, 5-bis(hydroxyimino)imidazolidine (LH2) has been prepared from anti-dichloroglyoxime, N,N′-diphenylmethylenediamine, and sodium bicarbonate in ethanol. Complexes of Cu(II), Ni(II), Co(II), Pd(II), and UO2(VI) and LH2 give a metal-ligand ratio of 1:2. A tetrahedral complex is obtained for the Ni(II) complex by coordination through N and O atoms. The (LH2)Co. H2O complex is squarepyramidal while the Cu(II), Pd(II) and UO2(VI) complexes are square-planar. The structures of the ligand and complexes are proposed based on elemental analysis, mass spectral, 1H-n.m.r., i.r., u. v. -visible, and magnetic data.

The Synthesis and Complex Formation of N-(2-Methylpyridyl)-aminoglyoxime

Abstract: N-(2-Methylpyridyl)aminoglyoxime (LH2) has been prepared from 2-(aminomethyl)pyridine and anti-chloroglyoxime in a mixture of chloroform and diethyl ether at -15°C with triethanolamine as the base. The structure of this ligand has been determined according to 1H n.m.r. and i.r. spectral data. LH2 gives a planar (LH2)Ni complex with slight octahedral distortion. In the Cu(II) complex, [(LH)ClCu], the N atom of the pyridyl group is also taking part in complex formation, the Cd(II) complex is binuclear, [(LH)Cl3(OH2Cd2] and the Zn(II) complex is ionic, [(LH2)ClZn]Cl. The uranyl complex is binuclear with hydroxo-bridges, [(LH)(UO2)(OH)2(UO2)(LH)]. The structures of the complexes have been proposed according to elemental analysis, magnetic measurements, i.r., and 1H n.m.r. data.

Synthesis of Some Isopropylphosphinoferrocenes

Abstract: The reactions of lithioferrocenes with chloroisopropylphosphines have been carried out to afford a series of new isopropylphosphinoferrocene derivatives including [1]-ferrocenophanes.

Synthesis and Structural Studies of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) Chelates Derived From Semicarbazide and Thiosemicarbazide Derivatives

Abstract: The synthesis and characterization of cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) chelates containing 1-anthranyl-4-phenyl-3-semicarbazide (APSC) and/or 1-anthranyl-4-phenyl-3-thiosemicarbazide (APTSC) are reported. The chelates have been characterized on the basis of elemental analyses, spectra (NMR, IR, visible), magnetic moments, conductivities and molecular weight measurements. The values of molar conductivities in DMP or DMSO indicate the non-ionic nature of all metal chelates. A tetrahedral structure is proposed for the Ni(II) chelates, square-planar for the Cu(II) chelates and tetrahedral or octahedral for the Co(II) chelates according to the data of magnetic measurements and electronic spectra. The ligands (APSC, APTSC) behave in a bidentate manner toward the metal ions, but with different coordination sites. 1HNMR spectra of the ligands and the diamagnetic chelates are discussed. The chelates have a monomeric or a polymeric nature.

Synthetic, Structural and Antifungal Studies of Some 3d-Metal Complexes of Salicylaldehyde-2-furanthiocarboxyhydrazone

Abstract: Salicylaldehyde-2-furanthiocarboxyhydrazone (H2L) forms the adducts Ni(H2L)2Cl2 and Cu(H2L)Cl2 and deprotonated complexes having a 1:1, 1:2 and/or 1:3 metal-to-ligand ratio. Magnetic and electronic spectral studies suggest octahedral geometry for VOL. 2H2O, Cr(HL)3, Ni(H2L)2Cl2, Co(HL)3, Co(HL) (L) and Cu(HL)2 and square planar geometry for all other Ni(II) and Cu(II) complexes. ESR spectral studies indicate a dxy ground state for VOL. 2H2O and dX2−y2 for Cu(II) complexes. Further the ESR data also suggest one and two nitrogen(s) are coordinated to the metal ion. 1H NMR studies of Zn(HL)2 suggest the deprotonation of the phenolic proton and the presence of a coordinated ethanol molecule in ZnL. EtOH. Infrared spectral studies show that H2L behaves as a neutral bidentate in the adducts, as a uninegative bidentate in 1:2 and 1:3 deprotonated complexes and as a binegative tridentate in 1:1 deprotonated complexes. The ligand and its 1:2 deprotonated complexes of Mn(II), Co(III) and Cu(II) have been t...

Improved Synthesis of Halo-Phosphorus(III) Fluorides

Abstract: An improved preparation of the P(III) fluorohalides, XPF2 (X = C1, Br) and of C12PF from the scrambling reaction of Et2NPF2 with PX3 (X = C1, Br) and of (Et2N)2PF with PC13, respectively, is described. An alternate synthesis of CIPF2 is based on a modification of the previously known P-N cleavage reaction of R2NPF2 with HC1. Characterization of the halophosphorus(III) fluorides, all previously known, was by 19F and 31P n.m.r. spectroscopy.

Nucleophilic Displacement of the Nitro Group in n6-Nitroarene-n5-cyclopentadienyliron Hexafluorophosphates

Abstract: The nitro group in n6-nitrobenzene or o-, m-, or p-nitrotoluene-n5 -cyclopentadienyliron hexaflurophosphate (I, II, III or IV, respectively) was shown to undergo readily nucleophilic displacement reactions when treated with an O, S or N containing nucleophile. The products obtained include the CpFe complexes of substituted arenes from reactions of I, II, III or IV with CH3OH, C2OH or p-CH3C6H4SH, all carried out in the presence of K2CO3, or with pyrrolidine.

Cobalt(II), Nickel(II) and Copper(II) Complexes of Schiff Bases Derived from Aminoacids and Acetylacetone

Abstract: New complexes of Co(II), Ni(II) and Cu(II) with Schiff bases obtained by the condensation of acetyl-acetone with glycine, β-alanine, L-leucine and DL-methionine have been synthesised and characterized by elemental analysis, molar conductance, magnetic, electronic, infrared spectral and thermalgravimetric analysis measurements. These complexes are non-electrolytes. Magnetic and spectral data indicate the Cu(II) complexes to be square planar and the Ni(II) and Co(II) complexes to be octahedral. All the Schiff bases coordinate through ONO donor sets derived from the carboxyl, imino and acetoxy groups:

Structural Studies of 1-Isatin-4-phenyl-3-thiosemicarbazone and 1 - (α-) Furyl-4-phenyl-3-thiosemicarbazone Complexes

Abstract: New metal complexes derived from 1-isatin-4-phenyl-3-thiosemicarbazone (IPTS) and 1-(α-) furyl-4-phenyl-3-thiosemicarbazone (PPTS) with Ni(II), Co(II), Cu(II) and Cd(II) have been synthesized and characterized on the basis of elemental analyses, magnetic moments, molar conductivities and spectral (NMR, Visible, IR) measurements. IR spectra show that IPTS coordinates in a tridentate manner via CN, CO and CS groups, while FPTS acts as a bidentate ligand coordinating via CN and CO groups. Magnetic and spectral studies suggest a square-planar structure for the Cu(II) and Ni(II) complexes which are derived from FPTS and a low-spin octahedral structure for [Co(FPTS-H)3]· 2H2O. On the other hand, octahedral structures are proposed for the complexes of Ni(II) and Cu(II) that are derived from IPTS and a low-spin octahedral structure for [Co(IPTS-H)2]. 1HNMR spectra of the ligands and the diamagnetic complexes are discussed.

Synthesis of Functional Methylphosphane-Borane Derivatives I. Convenient Syntheses of Tirmethylphosphane-Borane and Trimethylphosphane-Monohaloboranes

Abstract: Improved high-yield syntheses of trimethylphosphane-borane, -monochloroborane and -monobromoborane are described. The first process utilizes the reaction of trimethylphosphane with monoborane generated in situ. The latter preparations are by reaction of trimethylphosphane with the tetrahydrofuran adduct of monochloroborane and by the reaction of trimethyl-phosphane-borane with gaseous hydrogen bromide in solution, respectively.

Complexes of Zn(II), Cu(II), Ni(II) and Co(II) Tetrathiocyanato Mercurates(II) with Hydrazides and Their Biological Activity

Abstract: A new series of bimetallic tetrathiocyanate complexes of the type MM′(SCN)4.L, M = Zn(II), Cu(II), Ni(II), Co(II), M′ = Hg and L = benzoylhydrazide (BH), oxaldihydrazide (ODH) and malondihydrazide (MDH) have been synthesized in dilute ethanolic medium. The 1:1 metal:ligand complexes, which have been characterized by elemental analysis, magnetic moment data, electronic and infrared spectra, are insoluble in water as well as common organic solvents and decompose above 250°C without melting. The ligands act as bidentate coordinating species in the complexes. Some of these bimetallic complexes have been tested against Escherichia coli and Klebsillea pneumoniae bacteria and Aspergillus flavus, Penicillium sp. fungi, and were found to be biologically active.

Kinetics of Oxidation of Low Molecular Weight Alcohols by Potassium Ferrate

Abstract: Oxidation of simple alcohols by K2FeO4 is shown to follow a mixed order rate equation. The rate equation shows three terms, the first two terms being first order and second order in concentration of K2FeO4, respectively. The third term contains the conditional rate constant that depends on the concentration of the substrate (alcohol). This third term will also be shown to be first order dependent on K2FeO4 concentration.

Studies on Six-Coordinate Octahedral Chromium(III) Chelates with Schiff Bases Derived from 4-Acetyl-3-methyl-1-(3′-chloro Phenyl)-2-pyrazolin-5-one

Abstract: In the present paper 4-acetyl-3-methyl-1-(3′-chlorophenyl)-2-pyrazolin-5-one and its Schiff bases with o-toludine, m-toludine, p-toludine, m-chloro-aniline, p-chloroaniline and ethanolamine were employed in the preparation of chromium(III) chelates. All ligands are found to have bidentate coordinating ability. The complexes are six-coordinate and nonelectrolytes. Spectral parameters have been calculated from the visible reflectance spectra.

The Synthesis of Metallaindene and Metallafluorene Compounds

Abstract: The synthesis, spectra and properties of a series of metallaindenes (benzometalloles) and metallafluorenes (dibenzometalloles) have been investigated. Improved procedures for the formation of 1-lithio-1-phenyl-2-n-butyl-2-(2′-lithiophenyl)ethene from a reaction between n-butyllithium and diphenylacetylene have been achieved. Reactions of this dilithium intermediate with dimethyl- and diphenyldichlorosilane have afforded the respective benzosiloles in good yield. Reactions of the dilithium reagent with either dimethyltin dichloride or phenyldichlorophosphine produce the respective benzostannole and benzophosphole, whereas reactions with MCl4 (M = Si, Ge, Sn) result in formation of the corresponding metallacycles. Treatment of the benzophosphole with (n5-C5H5)Co(CO)2 or Fe3(CO)12 affords new organocobalt and -iron complexes which contain the benzophosphole ligand. The dilithium intermediate 1-lithio-1,2-diphenyl-2-(2′-lithiophenyl)ethene, prepared from phenyllithium and diphenylacetylene, reacts wi...

Synthesis and Structural Studies on Isomaleonitrile Dithiolates of Zn(II), Cd(II) and Hg(II) and Their Reaction Products with Ethylenediamine

Abstract: Isomaleonitrile dithiolates of the types M(i-MNT) and K2[M(i-MNT)2][M = Zn(II), Cd(II) or Hg(II); i-MNT = isomaleonitrile dithiolate (S2C:C(CN)2)2-] and their reaction products with ethylenediamine (en) have been isolated and characterized on the basis of analytical data, molar conductance, molecular weight, infrared and X-ray diffraction measurements. Tetrahedral coordination around M(II) in M(i-MNT), K2[M(i-MNT)2] and Zn(en) (i-MNT) and octahedral codrdination around M(II) in the other complexes has been proposed.

Syntheses and Characterization of Some Metal Complexes of 2,4-Dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one-thiosemicarbazone

Abstract: The complexation behaviour of 2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one thiosemicarbazone (DMPPOT) has been studied. Metal complexes of chromium(III), iron(III), palladium(II), cobalt(II), copper(II), nickel(II), manganese(II), zinc(II), cadmium(II), mercury(II), lead(II) and oxovanadium(IV) have been synthesised and characterised on the basis of elemental analysis, molecular weights, magnetic moments, infrared and electronic spectral studies, and conductance measurements. The complexes have been screened for their possible antimicrobial activity.

Synthesis and Characterization of 2-Thenoylhydrazine Complexes with some Bivalent Metal Ions

Abstract: The 2-thenoylhydrazine, TH(L) (Fig. 1) complexes having 1:1, 1:2 or 1:3 metal-ligand stoichiometry have been prepared and characterized by elemental analyses, molar conductance, molecular weight, magnetic susceptibility, electronic, infrared, NMR, Mossbauer and X-ray powder diffraction studies. Tetrahedral stereochemistry around Zn(II), Cd(II) and Hg(II), square pyramidal geometry around VO(IV) and octahedral coordination around Mn(II), Fe(II), Co(II), Ni(II) and Cu(II) ions have been proposed in these complexes on the basis of magnetic and spectral studies.

Organoxytitanium and Organotin Derivatives of Dibasic Tetradentate Chelating Disulphides

Abstract: The reaction between sulphur monochloride and salicylaldehyde has been found to give preferentially para-substituted bis(salicylaldehyde)disulphide, [C6H3(OH) (CHO)]2S2, A similar reaction has been observed in the case of ketonic phenols (2-hydroxyacetophenone, 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone) β-Diketones (acetylacetone, benzoylacetone, dibenzoylmethane, acetoacetanilide) give predominantly the enolised disulphide moiety However, bis(dibenzoylmethane)-disulphide has been found to exist in the ketonic form probably due to steric demand Coordination compounds of these disulphides with organotitanium(IV) and organotin(IV) have been synthesised and characterised; they are thermally stable polymeric substances The disulphides themselves are monomeric in boiling benzene

Coordination Compounds of Zirconium(lV) with Thiosemicarbazones

Abstract: The reactions of bis(cyclopentadienyl)dichloro zirconium(IV) with thiosemicarbazones have been studied in tetrahydrofuran in the presence of triethylamine or n-butylamine at room temperature. Complexes of the types : [(C5H5)2Zr(TSC)Cl], [(C5H5)Zr(TSC)3] and [(C5H5)2Zr(TSC')] (where TSCH is the monobasic thiosemicarbazone derived by the condensation of thiosemicarbazide with cinnamal-dehyde, benzaldehyde, acetophenone or p-hydroxy acetophenone and TSC'H2 is the dibasic thiosemicarbazone derived from thiosemicarbazide and salicylaldehyde)have been characterized by elemental analysis, magnetic susceptibility and conductance measurements and by electronic, ir. and 1H n.m.r. spectroscopy. Structures are proposed for these complexes.

Convenient and High-Yield Synthesis of Triphenylphosphine-Cyanoborane and -Dihaloboranes

Abstract: Triphenylphosphine-cyanoborane has been very conveniently prepared in high yield by the reaction of NaBH3CN with triphenylphosphine hydrochloride in refluxing tetrahydrofuran, and triphenylphosphine-dichloro- and dibromoboranes have been prepared by halogenation of the precursor triphenylphosphine-borane with free halogen respectively in carbon tetrachloride and dichloromethane. These compounds were characterized by elemental analysis, and infrared and proton NMR spectra.

The Synthesis of Dialkyldithiocarbamatogold(I) Dimers

Abstract: Several new dialkyldithiocarbamatogold(I) dimers of the type [Au(S2CNR2)]2, where R = i-butyl, n-octyl, n-dodecyl, cyclohexyl, benzyl, and allyl, and R2N = morpholino and piperidino, have been synthesized by the reaction, in water, of K[AuCl4] or H[AuCl4], Na2SO3, and NaS2CNR2. The complexes were characterized by IR spectroscopy, as well as elemental analysis and, where possible, mass spectral analysis.

Synthesis of 9,9′-Bis(m-Carboranyl) upon Catalytic Decomposition of 9,9′-Bis(m-Carboranyl) Mercury under Influence of (PPh3)3 RhCl

Abstract: A simple method is reported for the synthesis of 9,9-bis(m-carboranyl) from 9,9′-bis (m-carboranyl) mercury upon its decomposition under the influence of catalytic amounts of (PPh3)3RhCl in HMPA. Under these conditions, 9-m-carboranylmercury chloride easily forms 9-chloro-m-carborana and metallic mercury. A simple method for symmetrization of 9-o- and 9-m-carooranylmercury chloride into 9,9′-bis(o- and m-carboranyl)mercury under influence of sodium stannite in an alkaline medium was elaborated.

Synthesis and Structural Studies of Some First Row Transition Metal Complexes of N-Benzoylglycine Hydrazide

Abstract: N-Benzoylglycine hydrazide(BzGH) has been found to react with bivalent 3d-metal ions forming complexes of the types M(BzGH)2Cl2, M'(BzGH-H)2·nH2O and M' (BzGH-2H)·3H2O [M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); M' = Co(II), Ni(II) and Cu(II); n = 1 or 2]. Molar conductance studies in 0.001 M DMSO solutions have indicated the non-ionic nature of the complexes. High-spin octahedral geometry for Mn(II), Co(II) and Ni(II) complexes has been suggested on the basis of magnetic and/or electronic spectral studies. IR spectra suggest neutral bidentate, uninegative bidentate and dinegative tridentate behaviour of the ligand in the complexes. ESR spectra of Cu(II) complexes indicate a dx2-y2 ground state of the metal atom with a very weak metal-metal interaction in Cu(BzGH-H)2·H2O and Cu(BzGH-2H)·3 H2O.

Trans-[Selenocyanato(Imidazole)Bis(Dimethylglyoximato) Cobalt(III)] Complexes

Abstract: Imidazole(Im) or its derivatives react with Co(CNSe)2 and dimethylglyoxime (DH2) in EtOH in the presence of air to form mixed-ligand complexes of coba lt(III) of the type trans-[Co(DH)2(SeCN)(Im)]. These are non-electrolytic in DMF and Me OH and IR spectre provide evidence for the trans-structure as well as for the coordination of the selenocyenate ion through the Se-end.

Synthesis and Characterization of Cobalt(III) Complexes with Thiophene-2-carboxylaldehyde Thiosemicarbazone

Abstract: Cobalt(III) complexes of thiophene-2-carboxyal-dehyda thiosemicarbazone (ligand), of general formulae, Co(ligand)2.X3, Co(ligand)X3.H2O (where X = NO− 3, Cl−, Br−, I− and CH3COO−) and Co(ligand-H)3 have been prapared and characterised. The complexes are diamagnetic. Ligand field parameters have been calculated from the electronic spectra. IR spectra show that the ligand acts as a bidantats. Octahedral geometry has been suggested for all these complexes.

Nickel(II) and Copper(II) Complexes of the Schiff Base Derived from 2-(2-Aminophenyl)benzimidazole and 4-Hydroxybenzaldehyde

Abstract: Complexes of some Ni(Il) and Cu(Il) salts with the Schiff base derived from 2-(2-amino phenyl) benzimidazole and 4-hydroxybenzalde-hyde, L, have been prepared and characterised by magnetic susceptibility, IR, electronic and ESR spectral studies. They are of the general types CuL2X2(X = d, Br, CIO4 and 1/4SO4-H2O) and NILX2 (X = Cl, Br, NCS). IR spectra suggest that the Schiff base acts as bidentate ligand through the tertiary nitrogen of the imidazole ring and the exocyclic inline nitrogen. The results suggest octahedral geometry for the Cu(H) complexes, and a polymeric and dimeric nature for the NiLX2 (X = Cl, NCS) and NilBr2, respectively. © 1985, Taylor & Francis Group, LLC. All rights reserved.

Oxovanadium(V) Complexes With Nitrogen Donor Ligands

Abstract: The 1:1 and 2:3 molar reactions between oxovanadium(V) chloride and sodium salts of the nitrogen donor ligands (LH2) such as aldimines, ketamines, semicarbazones, thiosemicarbazones and azines in refluxing benzene have resulted in the formation of products of the type [(VOC1)(L)] and [(VO)2(L)3], respectively. These complexes were obtained in almost quantitative yields and are light grey to greyish-brown or black crystalline solids. These have been isolated and characterized by elemental analysis, molecular weight determinations, conductance and magnetic measurements and electronic, IR and 1H NMR spectral studies. These data suggest that the ligands are functioning as dibasic tridentate ligands towards the metal atoms, which have coordination numbers of five in both type of complexes with trigonal bipyramidal geometry.

A New Synthesis of TLI3 Complexes

Abstract: The following compounds Tll3.L2 (whereL=triphenylphosphine-oxide, hexamethylphosphorotriamide, pyridine N-oxide, 2-,3- or 4-methylpyridine N-oxide, 2-mercaptopyridine N-oxide and dimethylsulphoxide), have been prepared and characterized by elemental analysis. The solids are monomers and non-electrolytes in acetonitrile solution. Possible molecular structures are given on the basis of 1H NMR and IR spectra, with particular attention on the νTl-1 and νTl-0 stretching modes.

Synthesis and Characterization of the Complexes of N-Dimethylaminomethyl Isatin β-Thiosemicarbazone with Cobalt, Nickel, Copper, Zinc, Mercury and Iron Chlorides

Abstract: Complexes of N-Dimethylaminomethyl-isatin β thiosemicarbazone (C12H15N5OS) with Co(II),Ni(II),Cu(II), Hg(II) and Fe(III) have been prepared. The complexes were characterized by elemental analyses, molecular weight determination, conductance, magnetic moment measurement, electronic and i.r spectra. Complexes are of general formula M [L]2 where M = Co(II),Ni(II),Cu(II),Zn(II) and Hg(II) and M [L]2Cl where M = Fe(III). Cobait, copper, zinc and iron complexes are octahedral whereas nickel and mercury complexes are tetrahedrally coordinated. The i.r. spectra of the complexes indicate metal ligand bonding through sulphur, hydrazinic nitrogen and ketonic oxygen at ons of the ligand.

Synthesis and Physicochemical Properties of some Complexes of Aniline, p-Nitrosodimethylaniline and p-Nitrosodiethylaniline with Cadmium Halides and Sulphate

Abstract: Some intensely coloured complexes of p-nitrosodimethylaniline and p-nitrosodiethylaniline and colourless aniline complexes of cadmium halides and sulphate have been synthesized and characterized by their magnetic, conductance, and spectral measurements. Their conductance data show that they are non-electrolytes in nitromethane but dissociate appreciably in methanol. The molar magnetic susceptibilities indicate that they are diamagnetic with some evidence of polarization paramagnetism. Their electronic spectra in various solvents are dominated by an intense absorption around 400 nm due to the ligand which exhibited a bathochromic shift as the polarity of the solvent increased. The IR spectra indicate that the -NH2 group of aniline and the -N=O group of the nitrosodialkylanilines coordinate to the metal. Tetrahedral and octahedral coordination about the metal ion have proposed for the complexes.