Rhodium‐catalysed hydroformylation of 1‐octene using aryl and ferrocenyl Schiff base‐derived ligands

Monometallic and heterobimetallic complexes of Rh(I) bearing chelating N ,O ‐bidentate aryl‐ and ferrocenyl‐derived ligands have been synthesised via Schiff base condensation reactions, and characterised fully using ¹H NMR, ¹³C{¹H} NMR and Fourier transform infrared spectroscopies, elemental analysis and mass spectrometry. The new monometallic and heterobimetallic complexes were evaluated as potential catalyst precursors in the hydroformylation of 1‐octene at 95°C and 40 bar. The ferrocenylimine mononuclear compounds were inactive in the hydroformylation experiments. The Rh(I) monometallic and the ferrocene–Rh(I) heterobimetallic pre‐catalysts displayed good activity and conversion of 1‐octene as well as outstanding chemoselectivity towards aldehydes in the hydroformylation reaction.     

Efficient initiators for the ring‐opening polymerization of L‐lactide: Synthesis and characterization of NNO‐tridentate Schiff‐base zinc complexes

A series of efficient catalysts, based on zinc alkoxides coordinated with NNO‐tridentate Schiff‐base ligands (L¹H‐L⁶H), for ring opening polymerization of L ‐lactide have been prepared. The reactions of diethyl zinc (ZnEt₂) with L¹H‐L⁶H yielded [(μ‐L)ZnEt]₂ ( 1a–6a ), respectively. Further reaction of compounds 1a–6a with benzyl alcohol (BnOH) produced the corresponding compounds of [LZn(μ‐OBn)]₂ ( 1b–6b), respectively. X‐ray crystal structural studies reveal that all of these compounds 1a–6a are dimeric bridging through the phenolato oxygen atoms of the Schiff‐base ligand. However, the molecular structures of 1b–6b show a dimeric character bridging through the benzylalkoxy oxygen atoms. Ring‐opening polymerization of L ‐lactide, initiated by 1b–6b , proceeds rapidly with good molecular weight control and yields polymer with a very narrow molecular weight distribution. Experimental results show that the substituents on the imine carbon of the NNO‐ligand affect the reactivity of zinc complexes dramatically. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6466–6476, 2008     

Synthesis,spectroscopic, thermal analyses,biological activity and molecular docking studies on mixed ligand complexes derived from Schiff base ligands and 2,6‐pyridine dicarboxylic acid

Two novel Schiff base ligands (L^a and L^b) were prepared from the condensation of quinoline 2‐aldehyde with 2‐aminopyridine (ligand L^a) and from the condensation of oxamide with furfural (ligand L^b). Mixed ligand complexes of the type M⁺²L^a/b L^c were prepared, where (L^a and L^b) the primary ligands and L^c was 2,6‐pyridinedicarboxylic acid as secondary ligand. Metal ions used were Fe(II), Co(II), Ni(II) and Zn(II) for mixed ligands L^a L^c and Fe(II), Co(II), Ni(II), Cu(II), Hg(II) and Zn(II) for L^bL^c mixed ligands. L^a and L^b Schiff base ligands were both characterized using elemental analyses, molar conductance, IR, ¹H and ¹³C NMR. Mass spectra for L^b, [Zn(L^a)L^cCl]Cl and [Cu(L^b)L^cCl]Cl were also studied. ESR spectrum of the [Cu(L^b) L^cCl]Cl complex was also recorded The metal complexes were synthesized and characterized using elemental analyses, spectroscopic (IR, ¹H NMR, UV‐visible, diffused reflectance), molar conductance, magnetic moment and thermal studies. The IR and ¹H NMR spectral data revealed that 2,6‐pyridinedicarboxalic acid ligand coordinated to the metal ions via pyridyl N and carboxylate O without proton displacement. In addition, the IR data showed that L^a and L^b ligands behaved as neutral bidentate ligands with N₂ donation sites (quinoline N and azomethine N for L^a and two azomethine N for L^b). Based on spectroscopic studies, an octahedral geometry was proposed for the complexes. The thermal stability and degradation of the metal complexes were investigated by thermogravimetric analysis. The binding modes and affinities of L^a, L^b and Zn(II) complexes towards receptors of crystal structure of E. coli (PDB ID: 3 t88) and mutant oxidoreductase of breast cancer (PDB ID: 3 hb5) receptors were also studied. The antimicrobial activity against two species of Gram positive, Gram negative bacteria and fungi were tested for the Schiff base ligands, 2,6‐pyridinedicarboxylic acid and the mixed ligand complexes and revealed that the synthesized mixed ligand complexes exhibited higher antimicrobial activity than their free Schiff base ligands.     

Interaction of Mn(acac)3 with Asymmetrical Schiff Base Ligands containing an Amido Group

Interaction of asymmetrical Schiff base ligands H₃Lⁿ [where H₃Lⁿ are substituted 3–aza–4–(2–hydroxyphenyl)–N– (2–hydroxyphenyl)but–3–enamide] with Mn(acac)₃ (acac = acetylacetonate) has been investigated. Two different type of manganese(III) complexes have been obtained depending on the nature of the substituents on the ligand. We have found that ligands containing donor substituents drives to the formation of two different kinds of complexes from the same reaction: Mn(Lⁿ)(H₂O)_x ( 1a–5a ) and [Mn(HLⁿ)(acac)](H₂O)_y ( 1b–5b ) (where Lⁿ and HLⁿ signify the ligand in its trianionic and dianionic form, respectively). However, when the substituents are electron withdrawing or poor donor only compounds of the type [Mn(HLⁿ)(acac)](H₂O)_y ( 6–10 ) are obtained. All these compounds have been characterized by elemental analyses, IR and ¹H NMR spectroscopy, FAB mass spectrometry, magnetic measurements and molar conductivities. The electrochemical behaviour of these complexes has also been studied.     

Synthesis,structural characterization and biological activities of metal(II) complexes with Schiff bases derived from 5-bromosalicylaldehyde: Ru(II) complexes transfer hydrogenation

In this study, two novel Schiff base ligands (L¹ and L²) derived from condensation of methyl 2-amino-6-methyl-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate and methyl 2-amino-6-phenyl-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate, both starting matter with 5-bromo-salicylaldehyde, and their Zn(II) and Ni(II) metal complexes have been prepared using a molar ratio of ligand:metal as 1:1 except the Ru(II) complexes 1:0.5. The structures of the obtained ligands and their metal complexes were characterized by elemental analysis, FT-IR, ¹H NMR, ¹³C NMR, UV–vis, thermal analysis methods, mass spectrometry, and magnetic susceptibility measurements. Antioxidant and antiradical activity of Schiff base ligands and their metal complexes were been evaluated in vitro tests. Antioxidant activities of metal complexes generally were more effectives than free Schiff bases. 1c and 2c were used as catalysts for the transfer hydrogenation (TH) of ketones. 1c, 2c complexes were found to be efficient catalyst for transfer hydrogenation reactions.     

Synthesis,Electrochemical and Luminescence Studies of Nickel and Vanadium Complexes Containing Tetradentate Schiff Base Ligand with N2O2 Donor Atoms

A symmetrical tetradentate Schiff base ligand was derived by the condensation of ortho‐vanillin and thiourea in 2:1 molar ratio and adjusted pH. Nickel and vanadyl complexes were obtained using the template method by the reaction of ortho‐vanillin and thiourea with Ni(OAc)₂. 4H₂O and VO(acac)₂ (2:1:1 molar ratio) in absolute ethanol and adjusted pH. The Schiff base ligand and its complexes have been characterized by FT‐IR, ¹H NMR, UV/Vis, elemental analysis and conductometry measurements. In nickel and also vanadyl complexes the ligands were coordinated to the metals via the imine N and enolic O atoms. The complexes have been found to possess 1:1 metal to ligand stoichiometry and the molar conductance data revealed that the metal complexes were non‐electrolytes. The nickel and vanadyl complexes exhibited tetrahedral and square pyramidal coordination geometry, respectively. The emission spectra of the ligand and its complexes were studied in DMSO. Electrochemical properties of the ligand and its complexes were also investigated in the DMF solvent at the 150 mVs^‐1 scan rate. The ligand and its complexes showed irreversible processes at this scan rate.     

Effect of Heavy‐Atom (Br) at the Phenyl Rings of Schiff‐Base Ligands on the NIR Luminescence of their Bimetallic Zn‐Nd Complexes

Two heterobimetallic Zn‐Nd phenylene‐bridged Schiff‐base ligands complexes [ZnNd L¹ (Py)(NO₃)₃] ( 1 ) and [Zn L² Nd(Py)(NO₃)₃]·MeCN ( 2 ) (Py = pyridine, H₂L¹ = N,N′‐bis‐ (3‐methoxy‐salicylidene)phenylene‐1,2‐diamine, H₂L² = N,N′‐bis‐5‐bromo‐3‐methoxy‐salicylidene)phenylene‐1,2‐diamine) were obtained. Both 1 and 2 were structurally characterized by X‐ray crystallography, and their near‐infrared (NIR) luminescent properties were determined. For the two complexes, the occupation of pyridine at the axial position of 3d Zn²⁺ ions could effectively prevent luminescent quenching arising from OH‐, NH‐ or CH oscillators of the solvates around the 4f Nd³⁺ ions, and the heavy‐atom (Br) effect of the Schiff‐base ligands on their NIR luminescent properties is also discussed.     

Structural and spectroscopic characterization of a new luminescent NiII complex: bis{2,4‐dichloro‐6‐[(2‐hydroxypropyl)iminomethyl]phenolato‐κ3O,N,O′}nickel(II)

The design and preparation of transition‐metal complexes with Schiff base ligands are of interest due to their potential applications in the fields of molecular magnetism, nonlinear optics, dye‐sensitized solar cells (DSSCs), sensing and photoluminescence. Luminescent metal complexes have been suggested as potential phosphors in electroluminescent devices. A new luminescent nickel(II) complex, [Ni(C₁₀H₁₀Cl₂NO₂)₂], has been synthesized and characterized by single‐crystal X‐ray diffraction and elemental analysis, UV–Vis, FT–IR, ¹H NMR, ¹³C NMR and photoluminescence spectroscopies, and LC–MS/MS. Molecules of the complex in the crystals lie on special positions, on crystallographic binary rotation axes. The Ni^II atoms are six‐coordinated by two phenolate O, two imine N and two hydroxy O atoms from two tridentate Schiff base 2,4‐dichloro‐6‐[(2‐hydroxypropyl)iminomethyl]phenolate ligands, forming an elongated octahedral geometry. Furthermore, the complex exhibits a strong green luminescence emission in the solid state at room temperature, as can be seen from the (CIE) chromaticity diagram, and hence the complex may be a promising green OLED (organic light‐emitting diode) in the development of electroluminescent materials for flat‐panel‐display applications.     

Synthesis,characterization and biological studies of oxovanadium(IV) complexes with triazole‐derived Schiff bases

A series of triazole‐derived Schiff bases (L¹–L⁵) and their oxovanadium(IV) complexes have been synthesized. The chemical structures of Schiff bases were characterized by their analytical (CHN analysis) and spectral (IR, ¹H and ¹³C NMR and mass spectrometry) data, and oxovanadium(IV) complexes were elucidated by their physical (magnetic susceptibility and conductivity), analytical (CHN analysis), conductance measurements and electronic spectral data. The molar conductivity data indicate the oxovanadium(IV) complexes to be non‐electrolyte. The Schiff bases act as bidentate and coordinate with the oxovanadium(IV)‐forming stoichiometry of a complex as [M (L‐H)₂] where M = VO and L = L¹–L⁵ in a square‐pyramidal geometry. The agar well diffusion method was used for in vitro antibacterial screening against E. coli, S. flexenari, P. aeruginosa, S. typhi, S. aureus and B. subtilis and for antifungal activity against T. longifucus, C. albican, A. flavus, M. canis, F. solani and C. glaberata. The biological activity data show the oxovanadium(IV) complexes to be more antibacterial and antifungal than the parent Schiff bases against one or more bacterial and fungal strains. Copyright © 2009 John Wiley & Sons, Ltd.     

Antioxidative vs cytotoxic activities of organotin complexes bearing 2,6‐di‐tert‐butylphenol moieties

Two series of organotin(IV) complexes with Sn–S bonds on the base of 2,6‐di‐tert‐butyl‐4‐mercaptophenol ( L ¹ SH ) of formulae Me₂Sn(L¹S)₂ ( 1 ); Et₂Sn(L¹S)₂ ( 2 ); Bu₂Sn(L¹S)₂ ( 3 ); Ph ₂ Sn(L¹S)₂ ( 4 ); (L¹)₂Sn(L¹S)₂ ( 5 ); Me₃Sn(L¹S) ( 6 ); Ph₃Sn(L¹S) ( 7 ) (L¹ = 3,5‐di‐tert‐butyl‐4‐hydroxyphenyl), together with the new ones [Me₃SnCl(L²)] ( 8 ), [Me₂SnCl₂(L²)₂] ( 9 ) ( L ²  = 2‐(N‐3′,5′‐di‐tert‐butyl‐4′‐hydroxyphenyl)‐iminomethylphenol) were used to study their antioxidant and cytotoxic activity. Novel complexes 8 , 9 of Me_nSnCl_4 ? n (n = 3, 2) with Schiff base were synthesized and characterized by ¹H, ¹³C NMR, IR and elemental analysis. The crystal structures of compounds 8 and 9 were determined by X‐ray diffraction analysis. The distorted tetrahedral geometry around the Sn center in the monocrystals of 8 was revealed, the Schiff base is coordinated to the tin(IV) atom by electrostatic interaction and formation of short contact Sn–O 2.805 Å. In the case of complex 9 the distorted octahedron coordination of Sn atom is formed. The antioxidant activity of compounds as radical scavengers and reducing agents was proved spectrophotometrically in tests with stable radical DPPH, reduction of Cu²⁺ (CUPRAC method) and interaction with superoxide radical‐anion. Moreover, compounds have been screened for in vitro cytotoxicity on eight human cancer cell lines. A high activity against all cell lines with IC₅₀ values 60–160 nM was determined for the triphenyltin complex 7 , while the introduction of Schiff base decreased the cytotoxicity of the complexes. The influence on mitochondrial potential and mitochondrial permeability for the compounds 8 and 9 has been studied. It is shown that studied complexes depolarize the mitochondria but don't influence the calcium‐induced mitochondrial permeability transition.     

Ate Complexes in Iron‐Catalyzed Cross‐Coupling Reactions

Iron‐catalyzed cross‐coupling reactions have an outstanding potential for sustainable organic synthesis, but remain poorly understood mechanistically. Here, we use electrospray‐ionization (ESI) mass spectrometry to identify the ionic species formed in these reactions and characterize their reactivity. Transmetalation of Fe(acac)₃ (acac=acetylacetonato) with PhMgCl in THF (tetrahydrofuran) produces anionic iron ate complexes, whose nuclearity (1 to 4 Fe centers) and oxidation states (ranging from ?I to +III) crucially depend on the presence of additives or ligands. Upon addition of iPrCl, formation of the heteroleptic Fe^III complex [Ph₃Fe(iPr)]^? is observed. Gas‐phase fragmentation of this complex results in reductive elimination and release of the cross‐coupling product with high selectivity.     

Synthesis,spectral characterization and biological studies of transition metal(II) complexes with triazole Schiff bases

New metal based triazoles (1–12) have been synthesized by the interaction of novel Schiff base ligands (L¹–L³) with the Co(II), Ni(II), Cu(II) and Zn(II) metal ions. The Schiff base ligands and their all metal(II) complexes have been thoroughly characterized using various physical, analytical and spectroscopic techniques. In vitro bacterial and fungal inhibition studies were carried out to examine the antibacterial and antifungal profile of the Schiff bases in comparison to their metal(II) complexes against two Gram‐positive, four Gram‐negative and six fungal strains. The bioactivity data showed the metal(II) complexes to have more potent antibacterial and antifungal activity than their uncomplexed parent Schiff bases against one or more bacterial and fungal species. Copyright © 2012 John Wiley & Sons, Ltd.     

Mononuclear Pervanadyl (VO2+) Complexes with Tridentate Schiff Bases: Self‐assembling via C–H…oxo and π‐π Interactions

Pervanadyl (VO₂⁺) complexes with N‐(aroyl)‐N′‐(picolinylidene)hydrazines (HL = Hpabh, Hpath and Hpadh; H stands for the dissociable amide hydrogen) are described. The Schiff bases were obtained by condensation of 2‐pyridine‐carboxaldehyde with benzhydrazide (Hpabh), 4‐methylbenzhydrazide (Hpath) and 4‐dimethylaminobenzhydrazide (Hpadh), respectively. The reaction of [VO(acac)₂] and HL in acetonitrile in air affords the complexes of general formula [VO₂L]. The diamagnetic nature and EPR silence confirm the +5 oxidation state of vanadium in these complexes. Infrared spectra of the complexes are consistent with the enolate form of the coordinated ligands. Electronic spectra show charge transfer bands in the range 486–233 nm. The complexes are redox active and display an irreversible reduction (–0.64 to –0.72 V vs. Ag/AgCl). The crystal structures of all the complexes have been determined. In each complex, the metal centre is in a distorted trigonal‐bipyramidal N₂O₃ coordination sphere formed by the pyridine‐N, the imine‐N and the deprotonated amide‐O donor L^– and two oxo groups. The planar ligand satisfies one equatorial and two axial positions. The other two equatorial positions are occupied by the two oxo groups. In the solid state, the molecules of each of the three complexes form a chain‐like arrangement via the azomethine‐H…oxo interactions. Interchain weak π‐π interactions lead to two dimensional networks for [VO₂(pabh)] and [VO₂(path)]. On the other hand, [VO₂(padh)] forms a two‐dimensional network through interchain N‐methyl‐H…oxo interactions.     

Synthesis,characterization and catalytic properties of novel palladium(II) complexes containing aromatic sulfonamides: effective catalysts for the oxidation of benzyl alcohol

In this article, N‐(2‐aminophenyl)arylsulfonamides (1–5) were successfully synthesized by the reaction of o‐phenylenediamine and various benzenesulfonyl chlorides. The Schiff base derivatives (1a–f; 4e) of those compounds were obtained using different aldehydes. Then, a series of neutral‐four coordinate Pd(II) complexes (6–10) were prepared from the reaction of Pd(OAc)₂ and 1–5. On the other hand, when we tried to synthesize Pd(II) complexes containing Schiff base/sulfonamide ligands, two different situations were observed. Generally, when an electron‐donating group was attached to the imine fragment (1a–d) except for 1f, the Schiff base hydrolyzed and 6 was isolated. When an electron‐withdrawing group was attached to the imine fragment (1e, 4e), neutral four‐coordinate Pd(II) complexes (11–13) bearing Schiff base/sulfonamide ligands were isolated. The synthesized compounds were characterized by FT‐IR, elemental analysis and NMR spectroscopy. The complexes were used as a catalyst in the oxidation reaction of benzyl alcohol to benzaldehyde in the presence of H₅IO₆ in acetonitrile. All complexes showed satisfactory catalytic activity. The highest catalytic activity was obtained with 9. Copyright © 2012 John Wiley & Sons, Ltd.     

Ionic metallo‐Schiff base polymers of VO2+, Zn2+ and Cu2+: Synthesis,characterization and solid‐state conductivity

The viologen‐type dialdehyde of [N,N′‐bis(methylsalicylaldehyde)‐4,4′‐bipyridinium] dichloride (DA) was synthesized by reacting 5‐chloromethylsalicylaldehyde and 4,4′‐bipyridine. Then a new polymeric Schiff base ligand (PSBL) was synthesized by the condensation reaction of ethylenediamine and DA in methanol under reflux conditions. Afterwards, new ionic metallo‐Schiff base polymers (IMSPs) were synthesized by reacting PSBL with VO(acac)₂, ZnCl₂ and CuCl₂ via coordination chelation. DA, PSBL and IMSPs were characterized using various analytical methods and spectral techniques. The solid‐state electrical conductivities of PSBL and IMSPs were studied. The electrical conductivity of these polymers at 300 K ranged from 1.30 × 10^?5 to 4.52 × 10^?10 Ω^?1 m^?1, which means they are potential organic and metallo‐organic semiconductors.     

Synthese und Koordinationsverhalten neuer Schiffscher Basen aus 3‐Formylacetylaceton und natürlichen L‐Aminosäuren

Three novel chiral Schiff Base ligands (H₂L) were prepared from the condensation reaction of 3‐formyl acetylacetone with the amino acids L ‐alanine, L ‐phenylalanine, and L ‐threonine. X‐ray single crystal analyses revealed that the Schiff Base compounds exist as enamine tautomers in the solid state. The molecular structure of the compounds is stabilized by an intramolecular hydrogen bridge between the enamine NH function and a carbonyl oxygen atom of the pentandione residue. Treatment of the ligands H₂L with copper(II) actetate in the presence of pyridine led to the formation of copper complexes [CuL(py)]. In each of the complexes the copper atoms adopt a distorted square‐pyramidal coordination. Three of the basal coordination sites are occupied by the doubly deprotonated Schiff Bases L^2– which act as tridentate chelating O, N, O‐ligands. The remaining coordination sites are occupied by a pyridine ligand at the base and a carboxyl oxygen atom of a neighboring complex at the apical position. The latter coordination is responsible for a catenation of the complexes in the solid state.     

Synthesis of di‐nitrogen Schiff base complexes of methyltrioxorhenium(VII) and their application in epoxidation with aqueous hydrogen peroxide as oxidant

Several di‐nitrogen Schiff bases were synthesized through the condensation of 2‐pyridinecarboxaldehyde with primary amines. The Schiff bases as ligands coordinated with methyltrioxorhenium (MTO) smoothly to afford the correspondent complexes which were characterized by IR, ¹H NMR, ¹³C NMR, MS and elemental analysis. One of the complexes was analyzed by X‐ray crystallography as well. The results revealed that the complexes display distorted octahedral geometry in the solid state with a trans‐position of Schiff base. Catalytic results indicated that the complexes as catalysts increased the selectivity of epoxides remarkably compared with MTO in the epoxidation of alkenes with 30% hydrogen peroxide as oxidant and the increasing rate depended on the structure of the Schiff base ligands of the complexes. The results indicated that the stronger the donating ability of the ligand, the higher selectivity of epoxides the complex gave in the epoxidation of alkenes with 30% hydrogen peroxide as oxidant. Copyright © 2010 John Wiley & Sons, Ltd.     

New Schiff Bases Containing Silicon and Their Co(II) and Cu(II) Complexes: Synthesis,Complexation, Characterization,and Antimicrobial and Electrochemical Properties

Two novel Schiff base ligands, 4-((3-(trimethoxysilyl)propylimino)methyl)benzene– 1,2,3-triol (L¹H) and 4-((3-(triethoxysilyl)propylimino)methyl)benzene–1,2,3-triol (L²H), have been synthesized by the reaction of 2,3,4-trihydroxybenzaldehyde with 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane, respectively. The mononuclear Co^II and Cu^II complexes of these Schiff bases were prepared. The complexes of the Schiff bases are formed by coordination of N, O atoms of the ligands. The proposed structures were confirmed by elemental analyses, FT-IR, and UV-visible spectroscopy, magnetic susceptibility, and conductance measurements; the ¹H NMR spectra of the ligands were also recorded. The analytical data show that the metal to ligand ratio in the complexes containing silicon is 1:2. The electrochemical properties of the complexes have been investigated at 100 mVs^?1 scan rate in DMSO. In addition, the antimicrobial activity of L¹H and L²H Schiff ligands, and their [M(L¹)2] and [M(L²)2] type coordination compounds, were investigated.     

Synthesis,structural features and biochemical activity assessment of N,N′‐bis‐(2‐mercaptophenylimine)‐2,5‐thiophenedicarboxaldehyde Schiff base and its Co(II), Ni(II), Cu(II) and Zn(II) complexes

The tetradentate Schiff base ligand (SB), N,N′‐bis‐(2‐mercaptophenylimine)‐2,5‐thiophenedicarboxaldehyde was prepared via condensation of 2,5‐thiophene‐dicarboxaldehyde with 2‐aminothiophenol in a 1:2 molar ratio by conventional method. Additionally, its Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized and fully characterized by elemental analysis, FT‐IR, ¹H NMR, ¹³C NMR, UV–Vis, ESR, ESI‐mass, conductivity and magnetic susceptibility measurements. Spectral studies suggested that, the Schiff base coordinate metal ions through the azomethine N‐ and deprotonated thiol S‐ atoms. Based on UV–Vis absorption and magnetic susceptibility data, tetrahedral geometry was assigned for both Co(II) and Zn(II) complexes, whereas on the other hand, square planar geometry for both Ni(II) and Cu(II) complexes. The Schiff base and its metal complexes were screened for their in vitro antimicrobial activity by minimum inhibitory concentration (MIC) method. Free radical scavenging activity of the novel compounds was determined by elimination of 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) radicals. In addition, the interactions of the free ligand and its complexes with calf thymus DNA (CT‐DNA) were explored using absorption, emission and viscosity measurements techniques.     

Syntheses of Some New Group 4 non-Cp Complexes Bearing Schiff-base, Thiophene Diamide Ligands Respectively and Their Catalytic Activities for a-Olefin Polymerization

Totally sixteen new titanium and zirconium non-Cp complexes supported by Schiff-base, or thiophene diamide ligands have been synthesized. The complexes are obtained by the reaction of M(OPr-i)4(M=Ti,Zr) with the corresponding Schiff-base ligand in 1:1 molar ratio in good yield. The thiophene diamide titanium complex has been prepared from trimethylsilyl amine [N,S,N] ligand and TiCl4 in toluene at 120℃. All complexes are well charac-terized by ^1H NMR, IR, MS and elemental analysis. When activated by excess methylaluminoxane (MAO), complexes show moderate catalytic activity for ethylene polymerization, and complex If (R^1=CH3,R^2=Br) exhibits the highest activity for ethylene and styrene polymerization. When the complexes were preactivated by triethylaluminum (TEA), both polymerization activities and syndiotacticity of the polymers were greatly improved.