Glycol modified cis -diisopropoxy- bis ( N -phenylsalicylideneiminato)zirconium(IV): syntheses,characterization and low temperature transformation to nanocrystalline zirconia

Zr(OPrⁱ)₄·PrⁱOH reacts with N-phenylsalicylideneimine in anhydrous benzene in 1 : 2 molar ratio to afford [Zr{O(C₆H₄)CH=NPh}₂{OPrⁱ}₂] (1). Further reactions of 1 with various glycols yield heteroleptic complexes of the type [Zr{O(C₆H₄)CH=NPh}₂{O–G–O}] [where–G–= (CH₂)₂ (2), (CH₂CHCH₃) (3), (CH₃CHCHCH₃) (4), (CH₂CHC₂H₅) (5), (CH₂)₃ (6), (CH₂CH₂CHCH₃) (7), and (CH₂)₆ (8)]. All new derivatives have been characterized by elemental analyses, FTIR and NMR (¹H and ¹³C{¹H}) studies. FAB mass spectra of 1 and 7 revealed the monomeric nature of these complexes. Complete hydrolyses and low temperature transformations of 1 and 7 using Sol-Gel technique formed tetragonal phase of ZrO₂ at 700°C, whereas transformation of tetragonal to monoclinic phase occurred at 900°C. SEM observations of these samples indicate formation of agglomerates of nanocrystalline zirconia (Scherer analysis).     

SYNTHESIS AND ELECTROCHEMICAL PROPERTIES OF CYCLOPENTADIENYLIRON(II) COMPLEXES WITH BIS(DIPHENYLPHOSPHINO)AMINE AS LIGAND

Abstract

The synthesis and properties of new cationic iron(II) complexes of general formula [(η⁵-C₅H₅)FeL(η²-dppa)]A [A=I^?, L = CO(1); A = BF₄, L = CO(2) CH₃CN(4), η¹-dppa(5); dppa = NH(PPh₂)₂] are described. The carbonyl complex [(η⁵-C₅H₅)Fe(CO)(η²-dppa)]BF₄ is deprotonated to give the neutral complex [(η⁵-C₅H₅)Fe(CO){η²-(PPh₂)₂N}](3). All complexes have been characterized by elemental analysis and IR and NMR spectroscopies. Cyclic voltammetry of complexes 1–5 shows a diverse redox chemistry in acetonitrile solution. While the reduction of 1 and 2 leads to the formation of a dinuclear Fe(I) complex, 4 and 5 form mononuclear species of Fe(I); oxidation of metal centers of 1 and 2 is not observed and in complexes 3 and 4 the metal centers are oxidized at potentials < 1. Complex 5 in acetonitrile solution is transformed into complex 4.     

大环金属铜(II)、镍(II)配合物的模板合成与晶体结构

用模板法合成了1个大环金属铜(II)配合物[CuLCl₂]·3H₂O (1)和3个大环金属镍(II)配合物[NiLCl₂] (2)，[NiL](ClO₄)₂ (3)和[NiLH₂](ClO₄)₄ (4)(L=3,10-二乙基-1，3，5，8，10，12-六氮杂十四烷)，通过X-射线衍射单晶结构分析测定了它们的晶体结构。晶体结构显示：配合物1和2的金属离子与大环配体的4个氮原子及大环平面轴向的2个氯离子以八面体配位方式配位；配合物3和4的金属离子与大环配体的4个氮原子以平面正方形配位方式配位，配合物4的侧链氮原子的质子化导致侧链结构翻转，使得其侧链与大环平面共面。     

Syntheses,crystal structures,and antibacterial activities of manganese(III), nickel(II), and copper(II) complexes containing a tetradentate Schiff base

Three new mononuclear Schiff-base complexes, namely [Mn(L)Cl] (1), [Ni(L)] (2), and [Cu(L)] (3), where L?=?anion of [N,N′-bis(2-hydroxybenzophenylidene)]propane-1,2-diamine, have been synthesized by reacting equimolar amounts of the respective metal chloride and the tetradentate Schiff base, H₂L, in methanol. The complexes have been characterized by microanalytical, spectroscopic, single-crystal X-ray diffraction, and other physicochemical studies. Structural studies reveal that 1 adopts a distorted square-pyramidal geometry whereas 2 and 3 are isotypic with distorted square-planar geometries. The antibacterial activities of 1–3 along with their Schiff base have been tested against some Gram(+) and Gram(?) bacteria.     

Metal–organic supramolecular architectures derived from a new zwitterionic dicarboxylate ligand

A series of new coordination compounds with 1-carboxymethylpyridinium-4-benzoate (L) and transition metal ions have been synthesized. They are formulated as [M(L)₂(H₂O)₄]?·?4H₂O M=Mn (1) and Co (2), {[M(L)₂]?·?xH₂O} _n M=Mn, x?=?1 (3); M=Co, x?=?2 (4), and M=Cu, x?=?3 (5). In 1 and 2, the zwitterionic dicarboxylate ligand is monodentate through only one carboxylate to generate mononuclear molecules. The molecules are assembled through O–H?···?O interactions to give 3-D pillared layer-like architectures, in which interesting 1-D tape-like hydrogen bonding motifs are connected into 2-D layers via carboxylate-mediated hydrogen bonds. In 3–5, the organic ligands serve as bridges with one carboxylate monodentate and the other chelating, and the metal ions are linked by double bridges to give 1-D polymeric chains, which are zigzag (3) or stair-like (4 and 5) due to the cis or trans coordination geometry around metal ions. The chains are further stabilized and associated into 3-D architectures through intra- and interchain hydrogen bonding and/or π–π stacking interactions.     

Darstellung und Charakterisierung von Halogeno(diethyldithiocarbamato) (triethylphosphin)-nickel(II)-Komplexen

The complexes [Ni(PEt ₃)₂ dtc]X (1) and Ni(PEt ₃)Xdtc (2) (dtc=S₂CNEt ₂,X=Cl, Br, I) have been prepared. As conductivity, susceptibility, UV and IR measurements show, the cations [Ni(PEt ₃)₂ dtc]⁺ of1 and the complexes2 at ambient temperature have square-planar structure. We suppose there might exist an equilibrium for2 between square-planar and tetrahedral configuration.

     

Investigation of the Addition of Benzenethiol to p-Chlorophenylphenylacetylene

The addition of benzenethiol to p-chlorophenylphenylacetylene results in the formation of a mixture of two pairs of diastereomeric (E)- and (Z)-1-p-chlorophenyl-2-phenyl-1-phenylthioethylenes (1 and 2) and (E)- and (Z)-1-p-chlorophenyl-2-phenyl-2-phenylthioethylenes (3 and 4). The configurations of these compounds have been established by ¹ H NMR studies, by their preparation from benzyl p-chlorophenyl ketone and p-chloro-benzylphenyl ketone, and by the oxidation of the thioethylenes 1, 2, 3, and 4 to the corresponding sulphonylethylenes 5, 6, 7, and 8, respectively.     

The First Butyltin(IV) Homo- and Heterobimetallic Diethanolaminates

Equimolar reactions of BuSn(OPrⁱ)₃ with diethanolamines, RN(CH₂CH₂ OH) ₂ (abbreviated as RdeaH₂, where R = H or Me), afford dimeric isopropoxo-bridged six-coordinate butyltin(IV) complexes [{Bu(η³-Rdea)Sn(μ-OPrⁱ)}₂] (R = H ( 1 ), Me ( 2 )). Interactions between BuSn(OPrⁱ)₃ and diethanolamines (RdeaH₂) in a 1:2 molar ratio yield monomeric derivatives of the type [BuSn(Rdea)(RdeaH)] (R = H ( 3 ), R = Me ( 4 )). These homometallic complexes on 1:1 reactions with an appropriate metal alkoxide form monomeric heterobimetallic complexes of the type [BuSn (Rdea)₂ {M(OR′)_n}] (R = H, M = Al, R′ = Prⁱ, n = 2 ( 5 ); R = H, M = Ti, R = Prⁱ, n = 3 ( 6 ); R = H, M = Zr, R′ = Prⁱ, n = 3 ( 7 ); R = Me, M = Al, R′ = Prⁱ, n = 2 ( 8 ); R = Me, M = Ti, R′ = Prⁱ, n = 3 ( 9 ); R = Me, M = Ge, R′ = Et, n = 3 ( 10 )). The driving force behind this work was (i) to explore the utility of homometal complexes ( 1 ) –( 4 ) in assembling a metal alkoxide fragment via a condensation reaction and (ii) to gain insights into the structures of new compounds by NMR spectral data. All of these derivatives have been characterized by elemental analysis, spectroscopic (IR, NMR; ¹H, ²⁷Al, and ¹¹⁹Sn) studies, and molecular weight measurements. ¹¹⁹Sn NMR spectral studies indicate that both the homometallic ( 3 ) and ( 4 ) and heterobimetallic ( 5 ) – ( 9 ) complexes exist in a solution in an equilibrium of six- and five-coordinated tin(IV) species.     

PREPARATION AND MULTINUCLEAR NMR STUDY OF BENZOYL METHYLENE TRIPHENYLPHOSPHORNE AND BENZOYL METHYLENE TRI-N-BUTYLPHOSPHORANE PT (0) AND PD (0) COMPLEXES

The reactions of Pd (dba)₂ (dibenzylidene acetone palladium (0)) and Pt (dba)₂ (dibenzylidene acetone platinum (0)) with BPPY (Benzoyl Methylene Triphenylphosphorane) and BBuPY (Benzoyl MethyleneTri-n-butylphosphorane) in (1:2) ratios using tetrahydrofuran as solvent have yielded Pd (dba)(BPPY)₂ (1), [Pd (dba)(C(H)COPh(PPh₂-o-C₆H₄)][PPh₃CH₂COPh](2), Pd (dba)(BBuPY)₂ (3), and Pt (dba)(BPPY)₂ (4) complexes. Upon heating complex (1) in THF, a cyclization reaction occurred to give complex (2). The products (1), (2), (3), and (4) are studied by IR, ¹H, ³¹P, and ¹³C NMR technique.     

Binuclear aluminum complexes with amine–imine type ligands derived from 1,3-benzenedialdehyde: synthesis,structures and their catalytic properties in ring-opening polymerization

Reaction of 1,3-bis(imino)benzenes with a stoichiometric amount of LiAlH₄ in THF yields iminoaminobenzenes L1 and L2. Further reaction of iminoaminobenzenes L1 and L2 with an equivalent of AlR₃ in toluene affords macrocyclic binuclear aluminum complexes 1a, 1b, and 2a. These macrocyclic aluminum complexes were characterized by ¹H NMR, ¹³C NMR, and IR spectroscopy. The molecular structures of 1a, 1b, and 2a were further confirmed by X-ray crystallography. X-ray diffraction analysis revealed that 1a, 1b, and 2a adopted a distorted tetrahedral geometry around aluminum. These complexes have efficient activities toward ring-opening polymerization of ε-caprolactone in the presence of benzyl alcohol.     

The Synthesis and Properties of New Metal-free and Metallophthalocyanines Containing Four Diloop Macrocyclic Moieties

The synthesis and characterization of new metal-free (9) and metal-containing (Zn, Ni or Cu 10, 11, 12) derivatives of a symmetrically octasubstituted phthalocyanine derived from 21,22-dicyano-2,3,5,6,8,9,11,12,15,17,18,25,26,28-tetradecahydro[1,4,7,12] benzodioxadithiacyclotetradeceno[6,7-b][1,4,7,10,13]benzopentaoxacyclopentadecene (7), which was synthesized in a multi-step reaction sequence, have been described. The novel compouds have been characterized by a combination of elemental analysis, ¹H and ¹³C NMR, IR, UV–vis and MS spectral data.     

Three new coordination complexes of cobalt(III), manganese(II), and copper(II) with N,N,O-donor hydrazone ligands: syntheses and structural characterizations

Three new coordination complexes, 2{[Co(L¹)₂]ClO₄} · 0.5CH₃OH (1), [Mn(L²)₂] (2), and [Cu(HL²)(L²)]ClO₄ · 2H₂O (3) have been synthesized from two tridentate N,N,O-donor hydrazone ligands HL¹, 2-acetylpyridine-salicyloylhydrazone, and HL², 2-benzoylpyridine-salicyloylhydrazone, respectively and thoroughly characterized by elemental analysis, FT-IR, UV–Vis, electrochemical, and room temperature magnetic susceptibility measurements. Structures of the complexes have been unequivocally established by single crystal X-ray diffraction technique. Structural analysis reveals that 1 consists of two chemically similar but crystallographically independent cationic [Co(L¹)₂]⁺ units and 2 consists of a neutral [Mn(L²)₂] molecule while 3 consists of a cationic [Cu(HL²)(L²)]⁺ unit. Metal ions display distorted octahedral geometry in 1 and 2 while in 3 it shows a distorted square pyramidal geometry. Ligand conformations around the metal ions are stabilized by the presence of intra-ligand hydrogen bonding in all the complexes. Structure of 3 reveals that a perchlorate ion linked to the complex by hydrogen bonding via a water molecule.     

Syntheses,crystal structures and magnetic properties of heteronuclear bimetallic compounds of [Cu(pdc)2][M(H2O)5]·2H2O [M=Ni(II), Co(II), Mn(II); pdc=2,6-pyridinedicarboxylato]

The complexes [M(H₂O)₅][Cu(pdc)₂]·2H₂O [M=Ni(II) 1, Co(II) 2, Mn(II) 3; pcd=2,6-pyridinedicarboxylato] are prepared and their crystal structures, magnetic susceptibilities and UV-Visible properties reported. In all cases, the Cu(II) ion occupies the chelating site in the pdc ligand, while the M(II) occurs as a pentaaqua ion bridged to the [Cu(pdc)₂] moiety through a carboxylate as demonstrated by both UV-Visible spectroscopy and X-ray diffraction. Single crystal X-ray diffraction shows the three complexes to be isostructural. Weak antiferromagnetic interactions between the metal ions are observed in 1 and 3, while the magnetic behavior of 2 is dominated by single ion anisotropy.     

Two 3-D CdII/ZnII complexes based on mixed 1,1-cyclobutanedicarboxylate and 4,4′-bipyridine ligands

Two new 3-D complexes, [M(L)(4bpy)_0.5(H₂O)]_∞ [M = Cd (1) and = Zn (2)], based on mixed 1,1-cyclobutanedicarboxylic acid (H₂L) and 4,4′-bipyridine (4bpy) have been synthesized; 1 and 2 feature (3,4)-connected (6³)(6⁵.8) topological networks consisting of pillared 2-D [M(L)(H₂O)]_∞ layered motifs. Complexes 1 and 2 are photoluminescent materials.     

STRUCTURES OF PYRIDINE CARBOXYLATE COMPLEXES OF COBALT(II) AND COPPER(II)

Abstract

The syntheses and crystal structures of [Co(nic)₂(H₂O)₄] (1). [Co(iso)₂(H₂O)₄] (2). [Cu(nic)₂(H₂O)₄] (3), and [Cu(iso)₂(H₂O)₄] (4) (nic = nicotinate; iso = isonicotinate) are reported. Complex 1 crystallizes in monoclinic, space group C2/m with cell parameters a =14.150(4). b = 6.883(2)., c = 8.497(2) Å, β= 118.28(2)° and Z = 2. The other crystals. 2. 3. and 4. are all triclinic, Pī; a = 9.777(3), b = 6.348(4), c = 6.888(3)Å, a= 113.10(6)., β= 110.55(3). γ = 97.61(5)°, and Z=l for 2; a = 7.0281(4), b = 7.7176(6), c = 8.6978(7)Å, a = 68.103(7), β = 68.526(5), γ = 62.550(6)°, and Z=1 for 3; a = 9.1807(4), b = 6.3334(3), c = 6.8871(3)Å, a= 108.213(4), β = 99.433(4), γ= 105.190(4)°, and Z= 1 for 4. The arrangements around the metal ions are trans-octahedra with two pyridyl nitrogens and two aqua oxygens in the equatorial positions and two aqua oxygens in the axial positions, although the Cu(II) complexes show a larger Jahn-Teller distortion.     

An investigation of the thermal behavior of heterobimetallic species containing copper(II) and tetracyanopalladate(II)

Synthesis, characterization and thermal behavior of four compounds that have the general formula [Cu{Pd(CN)₄}(L)_x]_n, in which en=1,2-diaminoethane and pn=1,3-diaminopropane (L=en, x=1 (I); L=pn, x=1 (II); L=en, x=2 (III); L=pn, x=2 (IV)) were described in this work. The complexes were studied by elemental analysis, infrared spectroscopy (IR), differential thermal analysis (DTA) and thermogravimetry (TG) and the residues of the thermal decomposition were characterized by X-ray powder diffraction and found as a mixture of CuO and PdO. The stoichiometry of the compounds was established via thermogravimetric and elemental analyses and their structures were proposed as coordination polymers based on their infrared spectra. The following thermal stability sequence was found: IV<I=II<III.     

SYNTHESES AND MASS SPECTRAL REARRANGEMENTS OF UNSATURATED BIS-SULPHIDES AND BIS-SULPHONES

Abstract

The synthesis of (E)- and (Z)-1.2-bis(p-fluorophenylsulphenyl)stilbenes (2a and 2b) and 1,2-bis(p-fluorophenylsulphonyl)stilbenes (3a and 3b) was carried out and their configurations were consistent with their stereospecific synthesis. The isomeric 1,1-bis(p-fluorophenylsulphenyl)- and 1,1-bis(p-fluorophenylsulphonyl)-2,2-bis(phenyl)ethylenes (8 and 9) were also synthesised and configurations were established by degradative oxidation. Mass spectral rearrangements of all these compounds were examined. Mass spectra of 1,1-bis-sulphide and 1,1-bis-sulphone bears close relationship with those of (E)- and (Z)-isomeric counterparts. Smiles-type rearrangement observed in 1,2-bis-sulphides was absent in 1,2-bis-sulphones. McLafferty-type rearrangement involving hydrogen migration, from aryl group was noticed in both bis-sulphides and bis-sulphones. Vinyl migration to the sulphone oxygen predominates over aryl migration in three isomeric bis-sulphones.     

Synthesis,characterization, antimicrobial,DNA binding,and oxidative cleavage activities of Cu(II) and Co(II) complexes with 2-(2-hydroxybenzylideneamino)isoindoline-1,3-dione

(E)-2-(2-hydroxybenzylideneamino)isoindoline-1,3-dione (Hbid) was prepared by condensation of N-aminophthalimide and salicylaldehyde and characterized by elemental analysis, IR, ¹H-NMR, and mass spectral studies. Mononuclear complexes [(phen)Cu^II(μ-Hbid)₂H₂O] (1), [(phen)Co^II(Cl)₂(μ-Hbid)]6H₂O (2) (phen?=?1,10-phenanthroline) and binuclear complexes [Cu^II(μ-Hbid)]₂ (3), and [Co^II(μ-Hbid)]₂ (4) with Hbid were prepared and characterized by elemental analysis, IR, UV-Vis, molar conductance, and thermogravimetric (TG) techniques. DNA-binding properties of 1–4 were investigated by UV spectroscopy, fluorescence spectroscopy, and viscosity measurements. The results suggest that 1 and 2 bind to DNA by partial intercalation, whereas 3 and 4 find different groove-binding sites. The cleavage of these complexes with super coiled pUC19 has been studied using gel electrophoresis; all the complexes displayed chemical nuclease activity in the absence and presence of H₂O₂ via an oxidative mechanism. Complexes 1–4 inhibit the growth of both Gram-positive and Gram-negative bacteria.     

REACTION OF HINDERD α,β - UNSATURATED KETONES WITH 2,4-BIS(4-METHOXYPHENYL)-1,3,2,4- DITHIADIPHOSPHETANE-2,4-DISULFIDE

Abstract

Six new hindered α,β-unsaturated ketones (22c-h) were prepared. Though the reaction of α,β-unsaturated ketones (22a,b) with 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphet-ane-2,4-disultide (23) in refluxing benzene gave the corresponding 2-arylidene-1-thiotetral-one dimers (26a,b) and 3H-1,2-thiaphospholene-2-sulfides (28a,b), the reaction of hindered α,β-unsaturated ketones (22d-h) with 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphet-ane-2,4-disultide (23) in retluxing benzene gave only identified 3H-1,2-thiaphospholene-2-sulfides (28c-g).     

Synthesis,characterization, structural investigation,and antimicrobial studies of mononuclear Zn(II), Cd(II), and Ag(I) complexes of an N3O Schiff base

An N₃O Schiff base (L), 1?:?1 condensate of benzil monohydrazone and 4-pyridine carboxaldehyde, and its Zn(II), Cd(II), and Ag(I) complexes were synthesized and characterized by elemental analyses and various spectroscopic techniques. The crystal structures of [ZnL₂Br₂] (1), [CdL₂I₂]·CH₂Cl₂, (2)·CH₂Cl₂, and [Ag(L)₂]ClO₄ (3) have been determined using X-ray crystallography. The Zn(II) and Cd(II) complexes show a tetrahedral configuration whereas in the asymmetric unit of 3, two independent coordination units of Ag(I) are present. Carbonyl–silver interaction, weak C–H?O interaction, and also π–π interaction are present in 3 in the solid state. The synthesized complexes have antibacterial activity against Klebsiella pneumoniae 114, Escherichia coli K88, Salmonella typhi ATCC 34, Bacillus subtilis UC564, and Staphylococcus aureus ATCC25923. The results showed that in some cases the antibacterial activities of the complexes were comparable to standard antibiotics Tetracycline and Streptomycin. The antifungal activities of the complexes were also studied for Aspergillus niger, Aspergillus oryzae, Penicillium notatum, and Saccharomyces cerevisiae. MIC values of 1, 2·CH₂Cl₂, and 3 are less than the Nystatin standard.