Synthesis and spectral properties of europium phthalocyanine complexes

Methods for the synthesis of europium complexes with phthalocyanine and thenoyltrifluoroacetonate (tta) or ferrocenoyltrifluoroacetonate (fta) ligands are discussed. The spectral characteristics of the complexes PcEu(tta)(ttaH) and PcEu(fta)(ftaH) (Pc is phthalocyanine) are studied.     

Synthesis and spectral properties of lanthanide double-decker complexes with tetrabenzoporphyrin and phthalocyanine

Mixed-ligand double-decker complexes containing tetrabenzoporphyrin and phthalocyanine fragments were synthesized by reaction of phthalocyanine dilithium salt with tetrabenzoporphyrin complexes of lutetium, dysprosium, gadolinium, neodymium, and lanthanum. A relation was found between spectral parameters of the obtained sandwich complexes and radii of the central metal ions.     

Synthesis and spectral properties of isomers of cobalt tetrakis(dicyanophenoxy)phthalocyaninate

Russian Chemical Bulletin - 4,4´-[1,3-Phenylenebis(oxy)]- and 4,4´-(1,4-phenylenebis(oxy)]diphthalonitriles and the corresponding tetrasubstituted cobalt phthalocyaninates were...     

Sandwich complexes of yttrium, neodymium, gadolinium, and dysprosium with meso-trans-di(hexadecyl)-tetrabenzoporphyrin and phthalocyanine fragments. Synthesis and spectral properties

Sandwich-type asymmetric complexes of yttrium, neodymium, gadolinium, and dysprosium were synthesized by the reaction of the corresponding meso-trans-bis(hexadecyl)tetrabenzoporphyrinates with dilithium phthalocyianine. Spectral properties of these compounds were investigated.     

Synthesis,spectral, and catalytic studies of ruthenium(II) unsymmetrical Schiff-base complexes

Unsymmetrically-substituted ruthenium(II) Schiff-base complexes, [Ru(CO)(B)(L ^x )] [B = PPh₃, AsPh₃ or Py; L ^x = dianion of tetradentate unsymmetrical Schiff-base ligand; x = 4–7, L⁴ = salen-o-hyac, L⁵ = valen-o-hyac, L⁶ = salphen-o-hyac, L⁷ = valen-2-hacn], were prepared and characterized by analytical, IR, electronic, and ¹H NMR spectral studies. The new complexes were tested for their catalytic activity towards the oxidation of benzylalcohol to benzaldehyde.     

New phosphorus-containing metal phthalocyanine complexes. Synthesis and spectral and electrochemical studies

Hitherto unknown phosphorus-containing 4,5-bis(diethoxyphosphorylmethyl)- and 4-methyl-5-diethoxyphosphorylmethylphthalonitriles were synthesized starting from o-xylene. Their tetramerization afforded free phthalocyanine ligands and their complexes with Zn, Ni, Co, and a number of rare-earth metals. The spectral and electrochemical properties of the phthalocyanines synthesized were studied. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1634–1638, August, 2008.     

Synthesis, spectral and catalytic activity of some manganese(II) bis-benzimidazole diamide complexes

Four Mn(II) complexes bound to a neutral bis-benzimidazole diamide ligand N,N'-bis(2-methyl benzimidazolyl 2,2'-oxy-diethanamide) (GBOA) have been synthesized and characterized. Anionic ligand associated with the complexes varies as Cl- CH3COO-, SCN- and ClO4-. X-ray structure of one of the complexes [Mn(GBOA)2(H2O)2]Cl(2)·4H2O was solved and shows that the Mn(II) ion is hexacoordinate. Two equatorial positions are occupied by benzimidazole imine nitrogen atoms while the other two sites are occupied by amide carbonyl oxygens. The imine nitrogen and carbonyl oxygens are bound to Mn(II) by different arms of the two ligands while axial sites are occupied by two water molecules. Two Cl- anions are outside the coordination sphere and form an extensive 3D H-bonded network. Axially distorted octahedral geometry is confirmed for all the four complexes by low temperature EPR spectroscopy. Distortion parameter D was found to be similar for [Mn(GBOA)2(H2O)2]Cl(2)·4H2O and [Mn(GBOA)2(H2O)2]·(CH3COO)2·H2O. Cyclic voltammograms have been obtained for all the four complexes and E(1/2) values are dependent on the anionic ligand being in the coordination sphere or outside. [Mn(GBOA)2(H2O)2]Cl(2)·4H2O and [Mn(GBOA)2(H2O)2]·(CH3COO)2·H2O carry out the selective oxidation of N-benzyldimethylamine, and 1-methyl-pyrollidine to their respective carbonyl products with catalytic efficiency of 35-50%.     

Synthesis,spectral and thermal properties of poly(2-hydroxy-4-methacryloyloxybenzaldehyde)-metal complexes

2-Hydroxy-4-methacryloyloxybenzaldehyde (2H4MBA), prepared from methacryloyl chloride and 2,4-dihydroxybenzaldehyde, was polymerized in methyl ethyl ketone at 70°C using benzoyl peroxide as a free radical initiator. Polychelates were obtained from N,N-dimethylformamide solutions of poly(2H4MBA) on addition of aqueous solutions of Cu(II)/Ni(II) ions. The polymers and polychelates were characterized by elemental analyses and spectral studies. The IR spectra of these polychelates suggest that metals are coordinated through the oxygen of the aldehyde group and oxygen of the phenolic—OH group. The electronic spectra, EPR, and magnetic moments of polychelates showed an octahedral and square planar structure for poly(2H4MBA)-Ni(II) and poly(2H4MBA)-Cu(II) complexes, respectively. X-ray diffraction studies reveal that the polychelates are highly crystalline. The thermal properties of polymer-metal complexes and their catalytic activity are discussed. © 1996 John Wiley & Sons, Inc.     

Synthesis,spectral and thermal properties of macrocyclic zinc(II) complexes

The new zinc ternary complexes [Zn(cyclen)NO₃]ClO4 (I), [Zn₂(cyclen)₂(m-nic)](ClO₄)₃ (II), [Zn₂(cyclen)₂(m-pic)](ClO₄)₃ (III) (cyclen=1,4,7,10-tetraazacyclododecane; nic=nicotinic acid; pic=picolinic acid) were synthesized and their spectral and thermal properties were investigated. The compounds were characterized by elemental analysis, IR spectroscopy and TG/DTG, DTA methods. Moreover, the way of coordination of pyridinecarboxylate anions was proposed on the basis of the spectral data and consequently proved with results of X-ray structure analysis. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis,spectral characterization and catalytic applications of Ru(II) complexes with amide ligands

Ruthenium(II) complexes of the type, RuCl₂(NO)(PPh₃)(L₂) (where L = amide ligand) have been synthesized and characterized on the basis of their elemental analysis IR, ¹H-, ¹³C-, ³¹P-NMR spectra. Amide ligand behaved as a bidentate ligand. The probable structures of these complexes have been discussed. They were used as catalysts for the hydrolysis of drugs viz. rivastigmine tartrate and neostigmine bromide. The percent yields of hydrolyzed products of these drugs were determined spectrophotometrically.     

Synthesis, spectral characterization and catalytic studies of new ruthenium(II) chalcone thiosemicarbazone complexes

A series of new hexa-coordinated ruthenium(II) complexes of the type [Ru(CO)(EPh₃)(B)(L)] (E = P or As; B = PPh₃, AsPh₃ or Py; L = chalcone thiosemicarbazone) have been prepared by reacting [RuHCl(CO)(EPh₃)₂(B)] (E = P or As; B = PPh₃, AsPh₃ or Py) with chalcone thiosemicarbazones in benzene under reflux. The new complexes have been characterized by analytical and spectroscopic (IR, UV-vis, ¹H, ³¹P and ¹³C NMR) methods. On the basis of data obtained, an octahedral structure was assigned for all of the complexes. The chalcone thiosemicarbazones behave as dianionic tridentate O, N, S donors and coordinate to ruthenium via the phenolic oxygen of chalcone, the imine nitrogen of thiosemicarbazone and thienol sulfur. The new complexes exhibit catalytic activity for the oxidation of primary and secondary alcohols to their corresponding aldehydes and ketones and they were also found to be efficient catalysts for the transfer hydrogenation of carbonyl compounds.     

Synthesis, characterization, and catalytic properties of new half-sandwich zirconium(IV) complexes

A number of new half-sandwich zirconium(IV) complexes bearing N,N-dimethylaniline-amido ligands with the general formula Cp*ZrCl(2)[ortho-(RNCH(2))(Me(2)N)C(6)H(4)] [R = 2,6-Me(2)C(6)H(3) (1), 2,6-(i)Pr(2)C(6)H(3) (2), (i)Pr (3), (t)Bu (4)] were synthesized by the reaction of Cp*ZrCl(3) with the corresponding ortho-(Me(2)N)C(6)H(4)CH(2)NRLi. All new zirconium complexes were characterized by (1)H and (13)C NMR, elemental analyses and single crystal X-ray diffraction analysis. The molecular structural analysis reveals that the NMe(2) group does not coordinate to the zirconium atom in all cases. Complexes 1-4 all have a pseudo-tetrahedral coordination environment in their solid state structures and adopt a three-legged piano stool geometry for the zirconium atoms with the amide N atom and the two Cl atoms being the three legs and the Cp* ring being the seat. Variable-temperature (1)H NMR experiments for all complexes 1-4 were performed to investigate the possible intramolecular interaction between the N atom in the NMe(2) group and the central zirconium atom in solution. Upon activation with Al(i)Bu(3) and Ph(3)CB(C(6)F(5))(4), complexes 1-4 all exhibit moderate to good catalytic activity for ethylene polymerization and copolymerization with 1-hexene, producing linear polyethylene or poly(ethylene-co-1-hexene) with moderate molecular weight and reasonable 1-hexene incorporation.     

Synthesis,spectral, electrochemical and catalytic studies of new Ru(III) tetradentate Schiff base complexes

The synthesis and characterization of several hexa‐coordinated ruthenium(III) Schiff base complexes of the type [RuX(EPh₃)(L)] (X = Cl or Br; E = P or As; L = dianion of the tetradentate Schiff base) are reported. IR, EPR, electronic spectra and cyclic voltammetric data of the complexes are discussed. An octahedral geometry has been tentatively proposed for all of these complexes. The new complexes have been subjected to catalytic activity in the reaction of oxidation of alcohols in the presence of N‐methylmorpholine‐N‐oxide. Copyright © 2007 John Wiley & Sons, Ltd.     

Structures and magnetic properties of copper(II) complexes containing tetrakis(2-pyridyl)methane

We designed spiro-fused dinculear complexes using tetrakis(2-pyridyl)methane (py₄C) for the development of ground high-spin molecules. We attempted to prepare a dinuclear copper(II) complex [{Cu(hfac)₂}₂(py₄C)], where hfac stands for 1,1,1,5,5,5-hexafluoropentane-2,4-dionate, but we obtained [Cu(hfac)₂(py₄C)] and [Cu(hfac)(py₄C) · Cu(hfac)₃]. These molecular structures were determined by the X-ray crystal structure analysis.     

Synthesis and photosensitizing properties of fluoroalkoxyl phthalocyanine metal complexes

Nine fluoroalkoxyl phthalocyanine metal complexes (Zn, AlCl, Mg, Co, Cu, FeCl) were synthesized from 4-(polyfluoroalkoxyl) phthalic anhydride. The fat-soluble phthalocyanines were characterized by elemental analysis, IR, ¹H NMR and fast-atom-bombardment mass spectroscopy. Zinc and aluminum chloride complexes show higher photooxidation ability in solution containing 20% perfluorocarbons than in hydrocarbon solvents.     

Tetrakis(4-bromophenoxy)phthalocyanine,its metal complexes,and their sulfonated derivatives: the synthesis and spectral properties

Russian Chemical Bulletin - Tetrakis(4-bromophenoxy)phthalocyanine and its metal complexes (M = Mg, Co, Cu, Zn) were synthesized. Sulfochlorination of these compounds followed by hydrolysis of the...     

Synthesis,thermal, spectral and biological properties of zinc(II) 4-hydroxybenzoate complexes

New zinc(II) 4-hydroxybenzoate complex compounds with general formula [Zn(4-OHbenz)₂L_n]·xH₂O, where 4-OHbenz = 4-hydroxybenzoate; L = isonicotinamide, N-methylnicotinamide, N,N-diethylnicotinamide, thiourea, urea, phenazone, theophylline, methyl-3-pyridylcarbamate; n = 2, 3; x = 0–3, 5, were synthesized and characterised by elemental analysis, thermal analysis and IR spectroscopy. The thermal behaviour of the prepared compounds was studied by TG/DTG and DTA methods in argon atmosphere. The thermal decomposition of hydrated compounds started with dehydration. During the thermal decomposition, organic ligand, carbon monoxide, carbon dioxide and phenol were evolved. The final solid product of the thermal decomposition was zinc or zinc oxide. The volatile gaseous product, solid intermediate products and the final product of thermal decomposition were identified by IR spectroscopy, mass spectrometry, qualitative chemical analyses and X-ray powder diffraction method. The antimicrobial activity of zinc(II) carboxylate compounds was tested against various strains of bacteria, yeasts and filamentous fungi (S. aureus, E. coli, C. parapsilosis, R. oryzae, A. alternata, M. gypseum). The presence of zinc in complexes led to the increase in their antimicrobial activity in comparison with free 4-hydroxybenzoic acid.     

Synthesis,spectral, magnetic and electrochemical properties of new dimeric copper(II) complexes

Four new ligands, bis-[3,5-disubstituted-2-hydroxybenzyl]-N-alkylamines (L¹–L⁴) with three potential donor sites, capable of forming dimeric copper(II) complexes have been prepared. The dimeric nature of the complexes has been confirmed by FAB mass spectral studies. Molar conductance studies indicate that the complexes are neutral. Electrochemical studies indicate that the complexes undergo quasi reversible two step single electron transfers at negative potentials (E_pc¹=−0.34 to −0.48 V, E_pc²=−0.59 to −0.72 V). Variable temperature magnetic studies indicate that the complexes are antiferromagnetically coupled (−2J=290 to 400 cm⁻¹). ESR spectral studies in DMF indicate that the complexes are dimeric and undergo dissociation on addition of pyridine.     

Synthesis and photochromic properties of tetrakis(3,5-dimethyl-2-thienyl)- and tetrakis(2,5-dimethyl-3-thienyl)ethylenes

Tetrakis(3,5-dimethyl-2-thienyl)ethylene and tetrakis(2,5-dimethyl-3-thienyl)ethylene were obtained from the corresponding dithienyl ketones by the McMurry reaction. The photochromic properties of the compounds obtained were studied. Dedicated to the Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1177–1181, May, 2005.     

Synthesis, spectral characterization and redox properties of iron (II) complexes of 1-alkyl-2-(arylazo)imidazole

Iron (II) complexes of 1-alkyl-2-(arylazo)imidazoles (p-R-C₆H₄-N=N-C₃H₂NN-1-R′, R = H (a), Me (b), Cl (c) and R′ = Me (1/3), Et (2/4) have been synthesized and formulated astris-chelates Fe(RaaiR′) ₃ ²⁺ . They are characterized by microanalytical, conductance, UV-Vis, IR, magnetic (polycrystalline state) data. The complexes are low spin in character,t _2g ⁶ (Fe(II)) configurations.