新的聚苯乙烯负载锌化合物:高效苯酚氧化催化剂(英文)

The novel recyclable free –ONNO– tetradentate Schiff base ligand N,N′‐bis(2‐hydroxy‐3‐ methox‐ybenzaldehyde)4‐methylbenzene‐1,2‐diamine (3‐MOBdMBn) was synthesized. Complexation of this ligand with zinc(3‐MOBdMBn‐Zn) was performed, and the catalytic activity of the complex was evaluated. The polymer‐supported analog of this complex(P‐3‐MOBdMBn‐Zn) was synthesized, and its catalytic activity was studied. These free and polymer‐anchored zinc complexes were prepared by the reactions of metal solutions with one molar equivalent of unsupported 3‐MOBdMBn or P‐3‐MOBdMBn in methanol under nitrogen. The catalytic activity of 3‐MOBdMBn‐Zn and P‐3‐MOBdMBn‐Zn was evaluated in phenol oxidation. The activity of P‐3‐MOBdMBn‐Zn was signif‐icantly affected by the polymer support, and the rate of phenol conversion was around 50% for polystyrene‐supported 3‐MOBdMBn. The experimental results indicated that the reaction rate was affected by the polymer support, and the rate of phenol conversion was 1.64 μmol/(L·s) in the presence of polystyrene‐supported 3‐MOBdMBn.     

A new oxidovanadium(Ⅳ) Schiff base complex containing asymmetric tetradentate ONN0O0Schiff base ligand:Synthesis,characterization,crystal structure determination,thermal study and catalytic activity

After synthesis of an asymmetric tetradentate ONN0O0 Schiff base ligand(H2L) followed by reaction of the synthesized H2 L with an equimolar mixture of methanolic solutions of the VO(acac)2, a new oxidovanadium(IV) Schiff base complex(VOL) was synthesized. The Schiff base ligand and its complex were characterized by FT-IR and UV–vis spectra and C, H, N analysis. The crystal structure of VOL was also determined by single crystal X-ray analysis. The VOL complex crystallizes in monoclinic space group Cc. The Schiff base ligand acts as a tetradentate ligand through its two iminic nitrogens and two phenolic and acetylacetonate oxygens. Thermogravimetric analysis of the VOL showed that it decomposes in two steps and converts to mixed vanadium oxides at 477 8C. In addition, thermal decomposition of the VOL complex in air at 660 8C leads to formation of V2O5 nanoparticles with the average size estimated from XRD 49 nm. The catalytic activity of the VOL complex was investigated in the epoxidation reaction and different reaction parameters were optimized. The results showed that the cyclic alkenes were efficiently converted to the corresponding epoxides, whereas the VOL did not appreciably convert the linear alkenes.     

新的聚苯乙烯负载锌化合物:高效苯酚氧化催化剂(英文)

The novel recyclable free –ONNO– tetradentate Schiff base ligand N,N′‐bis(2‐hydroxy‐3‐ methox‐ybenzaldehyde)4‐methylbenzene‐1,2‐diamine (3‐MOBdMBn) was synthesized. Complexation of this ligand with zinc(3‐MOBdMBn‐Zn) was performed, and the catalytic activity of the complex was evaluated. The polymer‐supported analog of this complex(P‐3‐MOBdMBn‐Zn) was synthesized, and its catalytic activity was studied. These free and polymer‐anchored zinc complexes were prepared by the reactions of metal solutions with one molar equivalent of unsupported 3‐MOBdMBn or P‐3‐MOBdMBn in methanol under nitrogen. The catalytic activity of 3‐MOBdMBn‐Zn and P‐3‐MOBdMBn‐Zn was evaluated in phenol oxidation. The activity of P‐3‐MOBdMBn‐Zn was signif‐icantly affected by the polymer support, and the rate of phenol conversion was around 50% for polystyrene‐supported 3‐MOBdMBn. The experimental results indicated that the reaction rate was affected by the polymer support, and the rate of phenol conversion was 1.64 μmol/(L·s) in the presence of polystyrene‐supported 3‐MOBdMBn.     

A New Method of Synthesis of Azo Schiff Base Ligands with Azo and Azomethine Donors: Synthesis of N-4-Methoxy- benzylidene-2-(3-hydroxyphenylazo)-5-hydroxy- aniline and Its Nickel(II) Complex

A new method for the synthesis of azo Schiff an base ligand in which the azo and azomethine groups are coordination sites was developed through a Schiff base precursor. The precursor, N-4-methoxybenzylidene-3-hydroxy- phenylamine (SB) derived from 3-aminophenol was regioselectively coupled with a diazonium ion para to the hydroxyl group of the amine component of the Schiff base. The para selectivity was controlled by the directing effect of the hydroxyl group. The ligand and its nickel(II) complex were characterized by elemental analyses, IR and UV-Vis spectroscopy. The analytical and spectral data supported the mononuclear formulation of the complex with metal to ligand ratio (M∶L＝1∶2) and suggested a square planar geometry for the complex.     

SYNTHESIS, CHARACTERIZATION AND CATALYTIC ACTIVITY OF N,N‘-BIS(3-ALLYL SALICYLIDENE)ETHYLENEDIAMINE COBALT(II) SCHIFF BASE COMPLEX ANCHORED ON A NEW POLYMER SUPPORT

A new chelating polymer support has been prepared by suspension copolymeriz a tion of synthesized N,N‘-bis(3-allyl salicylidene)ethylenediamine monomer Schiff base (N,N‘-BSEDA) with styrene (St) and divinylbenzene (DVB) using azobisisobutyronitrile (AIBN) as initiator in the presence of poly(vinyl alcohol). The content and complexation ability of monomer Schiff base (N,N‘-BSEDA) for cobalt(II) ions in prepared crosslinked polymer beads have shown dependence on the amount of DVB used in reaction mixture. The amount of monomer Schiff base (N,N‘-BSEDA) in crosslinked beads showed a substantial decreasing trend at high concentration of DVB in the reaction mixture (＞ 1.5 mol dm-3), hence the efficiency of complexation (EC%) and cobalt(II) ion loading (EL%) of polymer beads showed a decreasing trend. The structure of monomer Schiff base (N,N‘-BSEDA) and its cobalt(II) complex on polymer support was elucidated by IR, UV and magnetic measurements. The catalytic activity of polymer bound cobalt(Ⅱ) Schiff base complex was evaluated by analyzing kinetic data of decomposition of hydrogen peroxide in the presence of either supported cobalt (II) complex or free cobalt(II) complex. The activation energy for the decomposition of hydrogen peroxide by polymer supported cobalt(II)complex was found to be low (33.37 kJ mol-l) in comparison with unsupported cobalt(II) complex (56.35 kJ mol-1). On the basis of experimental observations, reaction steps are proposed and a suitable rate expression derived.     

A New Method of Synthesis of Azo Schiff Base Ligands with Azo and Azomethine Donors： Synthesis of N-4-Methoxybenzylidene-2-（3-hydroxyphenylazo）-5-hydroxyaniline and Its Nickel（Ⅱ） Complex

A new method for the synthesis of azo Schiff an base ligand in which the azo and azomethine groups are coordination sites was developed through a Schiff base precursor. The precursor, N-4-methoxybenzylidene-3-hydroxyphenylamine （SB） derived from 3-aminophenol was regioselectively coupled with a diazonium ion para to the hydroxyl group of the amine component of the Schiff base. The para selectivity was controlled by the directing effect of the hydroxyl group. The ligand and its nickel（Ⅱ） complex were characterized by elemental analyses, IR and UV-Vis spectroscopy. The analytical and spectral data supported the mononuclear formulation of the complex with metal to ligand ratio （M ： L = 1 ： 2） and suggested a square planar geometry for the complex.     

A silica gel supported cobalt(Ⅱ) Schiff base complex as efficient and recyclable heterogeneous catalyst for the selective aerobic oxidation of alkyl aromatics

A silica gel supported cobalt(Ⅱ) Schiff base complex was synthesized and used for the oxidation of alkyl aromatics using molecular oxygen as an oxidant under atmosphere pressure.The catalyst shows a high conversion of alkyl aromatics and selectivity to benzylic ketones,and could be reused at least 5 times without significant loss of catalytic activity.     

Synthesis and structure of tetranuclear copper(Ⅱ) complex containing μ4-oxo bridge

A new dinucleating Schiff base ligand HL(L=C13H17N2O3) has been synthesised and characterized.The single crystal structure of its complex [L2Cu4O(AcO4)]·2H2O has beendetermined by X-ray diffraction methods.The result indicates that every Cu atom has its square pyramidal coordination polyhedron and there is a tetrahedral Cu4O core in the complex molecule.Its active sites where catalytic oxidation of dioxygen occurs have been inferred.     

–ONNO–四齿配体负载铜(Ⅱ)配合物的合成与结构研究:环二酯开环聚合的高效催化剂(英文)

The –ONNO– tetradentate Schiff base ligand N,N'-bis(2-hydroxy-3- methoxybenzaldehyde) benzene-1,2-diamine(HMBBD) has been synthesized. The ligand was attached to copper(Cu-HMBBD) in methanol under N_2 atmosphere to give a mononuclear complex. The reactivity of this complex in the ring-opening polymerization(ROP) of lactide has been studied. The complex has a square planner geometry, as determined by X-ray diffraction studies. The copper complex is highly active towards the ring-opening polymerization of lactide, and the rate of polymerization is heavily dependent on the initiator used. The copper complex allows controlled ring-opening polymerization, as shown by the linear relationship between the percentage conversion and the number average molecular weight. Based on the literature, a mechanism for the ROP of lactide has been proposed.     

非晶态金属-磷酸铝催化正庚醛和苯甲醛羟醛缩合制茉莉醛(英文)

Amorphous aluminophosphate (AlP) and metal‐aluminophosphates (MAlPs, where M=2.5 mol%Cu, Zn, Cr, Fe, Ce, or Zr) were prepared by coprecipitation method. Their surface properties and catalytic activity for the synthesis of jasminaldehyde through the aldol condensation of n‐heptanal and benzaldehyde were investigated. The nitrogen adsorption‐desorption isotherms showed that the microporosity exhibited by the aluminophosphate was changed to a mesoporous and macroporous structure which depended on the metal incorporated, with a concomitant change in the surface area. Temperature‐programmed desorption of NH3 and CO2 revealed that the materials possessed both acidic and basic sites. The acidic strength of the material was either increased or decreased depending on the nature of the metal. The basicity was increased compared to AlP. All the materials were X‐ray amorphous and powder X‐ray diffraction studies indicated the absence of metal oxide phases. The Fourier transform infrared analysis confirmed the presence of phosphate groups and also the absence of any M‐O moieties in the materials. The selected organic reaction occurred only in the presence of the AlP and MAlPs. The selectivity for the jasminaldehyde product was up to 75%with a yield of 65%. The best conversion of n‐heptanal with a high selectivity to jasminaldehyde was obtained with FeAlP as the catalyst, and this material was characterized to have less weak acid sites and more basic sites.     

Dioxomolybdenum(VI) complexes of hydrazone phenolate ligands - syntheses and activities in catalytic oxidation reactions

The new cis-dioxomolybdenum (VI) complexes [MoO₂(L²)(H₂O)] (2) and [MoO₂(L³)(H₂O)] (3) containing the tridentate hydrazone-based ligands (H₂L² = N'-(3,5-di-tert-butyl-2-hydroxybenzylidene)-4-methylbenzohydrazide and H₂L³ = N'-(2-hydroxybenzylidene)-2-(hydroxyimino)propanehydrazide) have been synthesized and characterized via IR, ¹H and ¹³C NMR spectroscopy, mass spectrometry, and single crystal X-ray diffraction analysis. The catalytic activities of complexes 2 and 3, and the analogous known complex [MoO₂(L¹)(H₂O)] (1) (H₂L¹ = N'-(2-hydroxybenzylidene)-4-methylbenzohydrazide) have been evaluated for various oxidation reactions, viz. oxygen atom transfer from dimethyl sulfoxide to triphenylphosphine, sulfoxidation of methyl-p-tolylsulfide or epoxidation of different alkenes using tert-butyl hydroperoxide as terminal oxidant. The catalytic activities were found to be comparable for all three complexes, but complexes 1 and 3 showed better catalytic performances than complex 2, which contains a more sterically demanding ligand than the other two complexes.     

Catalytic efficacy of Schiff-base copper(II) complexes: Synthesis,X-ray structure and olefin oxidation

Three copper(II) Schiff-base complexes, [Cu(L¹)(H₂O)](ClO₄) (1), [Cu(L²)] (2) and [Cu(L³)] (3) have been synthesized and characterized [where HL¹ = 1-(N-ortho-hydroxy-acetophenimine)-2-methyl-pyridine], H₂L² = N,N′-(2-hydroxy-propane-1,3-diyl)-bis-salicylideneimine and H₂L³ = N,N′-(2,2-dimethyl-propane-1,3-diyl)-bis-salicylideneimine]. The structure of complex 1 has been determined by single crystal X-ray diffraction analysis. In complex 1, the copper(II) ion is coordinated to one oxygen atom and two nitrogen atoms of the tridentate Schiff-base ligand, HL¹. The fourth coordination site of the central metal ion is occupied by the oxygen atom from a water molecule. All the complexes exhibit high catalytic activity in the oxidation reactions of a variety of olefins with tert-butyl-hydroperoxide in acetonitrile. The catalytic efficacy of the copper(II) complexes towards olefin oxidation reactions has been studied in different solvent media.     

Synthesis and crystal structures of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>'-bis(5-methylsalicylidene)ethane-1,2-diamine and its bromido-, phenolato-, and dicyanoamido-cobridged polymeric copper(II) complex

A bis-Schiff base N,N'-bis(5-methylsalicylidene)ethane-1,2-diamine (H₂L) was prepared and characterized by elemental analysis, ¹H NMR and ¹³C NMR spectra, MS, and single crystal X-ray diffraction (CIF file CCDC no. 1022761 (H₂L)). Reaction of the Schiff base with copper bromide and sodium dicyanoamide in methanol gave a novel bromido-, phenolato-, and dicyanoamido-cobridged polymeric copper(II) complex, ({Cu₂LBr[N(CN)₂]}₂)_n (I). Structure of complex I was characterized by elemental analysis and single crystal X-ray diffraction (CIF file CCDC no. 1022762 (I)). The smallest repeat unit of complex I is a dicyanoamide bridged tetranuclear copper(II) complex moiety, {Cu₂LBr[N(CN)₂]}₂, in which there possesses a crystallographic inversion symmetry. The tetranuclear moieties are further linked through Br atoms, forming a zigzag chain. The chains are further linked by dicyanoamide ligands, forming a 2D network. One Cu atom in complex I is coordinated by two N and two O atoms of the Schiff base ligand and one Br atom, forming square pyramidal geometry. The other Cu atom is coordinated by two N atoms of the Schiff base ligand, two N atoms of dicyanoamide ligands, and one Br atom, forming square pyramidal geometry. The bromido-, phenolato-, and dicyanoamido-cobridged Cu···Cu distances are 4.823(2), 2.955(1), and 7.121(3) Å, respectively. The [Cu₂L] units are linked by the bridging groups, to form 2D chains along the xy plane.     

Synthesis and characterization of insoluble cobalt(II), nickel(II), zinc(II) and palladium(II) Schiff base complexes: Heterogeneous catalysts for oxidation of sulfides with hydrogen peroxide

The condensation reaction of 1,2-bis(2′-aminophenoxy)benzene with 2-pyridinecarbaldehyde in a mole ratio of 1:2 gives a new Schiff base ligand (L). Four Schiff base complexes, CoL(NO₃)₂ (1), NiLCl₂ (2), ZnL(NO₃)₂ (3) and Pd₂LCl₄ (4) have been prepared by direct reaction of the ligand (L) and appropriate metal salts. The Schiff base ligand (L) has been characterized by IR, ¹H NMR and ¹³C NMR spectroscopy and elemental analysis. Also, all complexes have been characterized by IR and XRD spectroscopy techniques and elemental analysis. The synthesized complexes have very poor solubility in all polar and non-polar solvents such as: H₂O, MeOH, EtOH, CH₃CN, DMSO, DMF, CHCl₃, CH₂Cl₂, THF, etc; therefore, they have been used as heterogeneous catalysts. Catalytic performance of the complexes was studied in oxidation of thioanisole using hydrogen peroxide (H₂O₂) as the oxidant. Various factors including the reaction temperature, amount of oxidant and catalyst amount were optimized. The palladium Schiff base complex, Pd₂LCl₄ (4), shows better catalytic activity than other complexes. Therefore, the Pd(II) Schiff base complex has been used as a catalyst for oxidation of different sulfides to their corresponding sulfones in acetonitrile with hydrogen peroxide as the oxidant. The palladium Schiff base complex, Pd₂LCl₄ (4), has shown a very good recyclability, up to five times, without any appreciable decreases in catalytic activity and selectivity.     

Synthesis and Characterization of Binuclear (μ-Oxalato) Copper(II) Complexes with N,N′-Diethylethylenediamine or N,N,N′-Trimethylethylenediamine

Three new binuclear w -oxalato copper(II) complexes of composition [(Cu(N,N' -dieten) H₂O)₂ox](ClO₄)₂ ·H₂O (1) (N,N'-dieten = N,N'-diethylethylenediamine, H₂ox = oxalic acid), [(Cu(trimeen)H₂O)₂ox](ClO₄)₂·2H₂O (2) (trimeen = N,N,N'-trimethylethylenediamine) and [(Cu(trimeen)H₂O)₂ox](NO₃)₂ ·2H₂O (3) have been isolated from the reactions of Cu(ClO₄)₂ ·6H₂O (or Cu(NO₃)₂ ·3H₂O), the appropriate amine and Na₂ox in water and have been characterized by IR and electronic spectroscopy and magnetic measurements. The crystal structure of [(Cu(N,N' -dieten)H₂O)₂ ox](ClO₄)₂.H₂O (1) has been determined by single-crystal X-ray analysis. The structure of ( 1 ) consists of binuclear cations [(N,N'-dieten)H₂O)Cu(ox)Cu(N,N'-dieten)H₂O)]²⁺, perchlorate anions and water molecules of crystallization. The copper atom is coordinated by two oxygen atoms of the oxalato ligand, two nitrogen atoms belonging to N,N'-dieten and one oxygen atom of water in a distorted square-pyramidal arrangement. The temperature dependence of magnetic susceptibilities (78-293 K) was measured for 1-3 . Magnetochemical measurements show that copper(II) ions in these compounds are antiferromagnetically coupled with J = -172 cm^-1, -172 cm^-1 and -168 cm^-1 (H = -2JS ₁ S ₂, S ₁= S ₂ = 1/2) for 1, 2 and 3, respectively.     

Synthesis,structural characterization and catalytic activity study of Mn(II), Fe(III), Ni(II), Cu(II) and Zn(II) complexes of quinoxaline-2-carboxalidine-2-amino-5-methylphenol: Crystal structure of the nickel(II) complex

Five new transition metal complexes [MnL(OAc)]·H₂O (1), [FeLCl₂] (2), [NiL₂]·H₂O (3), [CuLCl] (4) and [ZnL₂]·2H₂O (5) have been synthesized using a tridentate Schiff base ligand, HL (quinoxaline-2-carboxalidine-2-amino-5-methylphenol) and the complexes have been characterized by physicochemical and spectroscopic techniques. The spectral analyses reveal an octahedral geometry for 3, square pyramidal structure for 2 and square planar structure for 4. Analytical and physicochemical data indicate tetrahedral structure for 1 and octahedral structure for 5. The crystallographic study reveals that [NiL₂]·H₂O shows distorted octahedral geometry with a cis arrangement of N₄O₂ donor set of the bis Schiff base and exhibits a two-dimensional polymeric structure parallel to [0 1 0] plane. The complexes were screened for catalytic phenol hydroxylation reaction. Coordinatively unsaturated manganese(II), iron(III) and copper(II) complexes were found to be active catalysts. The poor catalytic activity of the nickel(II) complex is due to coordinatively saturated octahedral nature of the complex. Maximum conversion of phenol was observed for the copper(II) complex and the major product was catechol.     

Zeolite-Y enslaved manganese(III) complexes as heterogeneous catalysts

Traditional catalytic procedures for oxidation of phenol produce environmentally undesirable wastes. As a consequence, there is a clear demand for development of an environmentally benign catalytic route for the selective oxidation of phenol. A series of zeolite-Y enslaved Mn(III) complexes with Schiff bases derived from vanillin furoic-2-carboxylic acid hydrazone (VFCH), vanillin thiophene-2-carboxylic acid hydrazone (VTCH), ethylvanillin thiophene-2-carboxylic acid hydrazone (EVTCH), and/or ethylvanillin furoic-2-carboxylic acid hydrazone have been synthesized and characterized by physico-chemical techniques. Catalytic oxidations of phenol using 30% H₂O₂ as an oxidant over [Mn(VTCH)₂·2H₂O]⁺-Y, [Mn(VFCH)₂·2H₂O]⁺-Y, and [Mn(EVTCH)₂·2H₂O]⁺-Y under mild conditions were studied. These zeolite-Y enslaved Mn(III) complexes are stable and recyclable under current reaction conditions.     

Synthesis, characterization and structures of copper(II) complexes containing carboxylate and sulfonate groups

Four copper(II) complexes containing Schiff base and reduced Schiff base ligands derived from pyridine-2-aldehyde and amino acid containing carboxylate and sulfonate functional groups (N-(2-pyridylmethylene)-amino acid and N-(2-pyridylmethyl)-amino acid, (amino acids = ??-alanine and aminoethanesulfonic acid) namely, [Cu(Pbals)(H₂O)₂]ClO₄·H₂O 1, [Cu(Pbal)(ClO₄)(H₂O)] 2, [Cu₂(Paes)₂(ClO₄)₂]·2H₂O 3, and [Cu(Pae)(H₂O)]·ClO₄·H₂O 4 have been synthesized and characterized. The structural features of carboxylate and sulfonate donor groups have been elucidated. These copper(II) complexes demonstrate different coordination behaviour of the carboxylate and sulfonate groups. Carboxylate groups in complexes 1 and 2 bridge the metal centers and facilitate the formation of 1D helical coordination polymeric structures. In compound 3, the sulfonate groups bridge the metal centers to form a discrete dinuclear complex. In 4, the sulfonate groups link the neighbouring metal centers to form a 1D coordination polymeric structure.     

Selective and solventless oxidation of organic sulfides and alcohols using new supported molybdenum (VI) complex in microwave and conventional methods

A new dioxo-molybdenum (VI) complex supported on functionalized Merrifield resin ( MR-Mo ) has been synthesized and characterized by elemental, scanning electron mcroscopy, energy-dispersive X-ray analysis, TGA, Brunauer–Emmett–Teller method, powder-X-ray diffraction, Fourier transform infrared, X-ray photoelectron spectroscopy and DRS–UV–vis analysis. The virgin Merrifield resin ( MR ) was functionalized by carbonylation followed by Schiff base formation with ethanolamine ( MR-SB ). Experimental data showed that the Schiff base coordinated with the MoO₂²⁺ moiety via O- and N-atoms. The catalytic activity of MR-Mo was explored under solventless conditions toward the oxidation of organic sulfides and alcohols using 30% aqueous H₂O₂ as oxidant. The oxidation reactions were conducted under microwave and conventional methods. The microwave-assisted oxidation reactions were found to be many times faster than the conventional methods. The oxidation reactions were selective and formed sulfoxides or aldehydes as the sole product with superior TOF values among the molybdenum (VI)-based complexes. Besides these, the MR-Mo was purely heterogeneous in nature and can be recycled for at least five reaction cycles without the loss of catalytic efficiency and product selectivity.     

Synthesis and structural characterization of nickel(II), copper(II) and zinc(II) complexes with the hexadentate ligand 2,13-bis(2-pyridylmethyl)-3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane

The complexes [Ni(L²)]Cl₂·10H₂O (1), [Cu(L²)](ClO₄)₂·3H₂O (2), [Cu₂(L²)(H₂O)₂Cl₂]Cl₂ (3) and [Zn(L²)]Cl₂·10H₂O (4) (L²=2,13-bis(2-pyridylmethyl)-3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18,0^7.12]docosane) have been synthesized and characterized by X-ray crystallography, electronic absorption, ¹³C NMR and magnetic susceptiblity as well as cyclic voltammetry. The crystal structures of 1 and 4 show that the metal ion has a slightly distorted octahedral geometry with two nitrogen atoms of the pendant arms at the axial positions. However, 2 exhibits a square-planar geometry, coordinated by secondary and tertiary nitrogen donors of the macrocycle. Furthermore, 3 reveals a binuclear structure and a center of symmetry in which the each copper ion is coordinated by a distorted square-pyramidal geometry with an N₃Cl basal plane and a water molecule in the apical position. The magnetic behavior for 3 shows that a ferromagnetic interaction between the copper(II) ions is predominant at intermediate temperature and then a weaker antiferromagnetic coupling is involved at lower temperature. Cyclic voltammetric studies for 1–3 indicate that 1 undergoes quasi-reversible one-electron oxidation to the Ni(III) and reversible one-electron reduction to the Ni(I), 2 undergoes a irreversible one-electron reduction to the Cu(I) state, while 3 undergoes an overall quasi-reversible two-electron reduction to the binuclear Cu(I) complex.