Synthesis, characterization of cobalt(II) complex nanoparticles encapsulated within nanoreactors of zeolite-Y and their catalytic activities

Cobalt(II) complex nanoparticles of [14]aneN₄: 1,5,8,12-tetraaza-2,9-dioxo-4,11-diphenylcyclotetradecane; [16]aneN₄: 1,5,9,13-tetraaza-2,10-dioxo-4,12-diphenylcyclohexadecane; Bzo₂[14]aneN₄: dibenzo-1,5,8,12-tetraaza-2,9-dioxo-4,11-diphenylcyclotetradecane and Bzo₂[16]aneN₄: dibenzo-1,5,9,13-tetraaza-2,10-dioxo-4,12-diphenylcyclohexadecane have been encapsulated in the nanopores of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)cobalt(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, 1,3-diaminobenzene); [Co(N–N)₂]²⁺–NaY; in the nanopores of the zeolite-Y, and (ii) in situ condensation of the cobalt(II) precursor complex with ethylcinnamate. The new complex nanoparticles entrapped in the nanoreactor of zeolite-Y were characterized by several techniques: BET, chemical analysis and spectroscopic methods (FT-IR, UV–vis, XRD, and DRS). These complexes (neat and encapsulated) were used for epoxidation of styrene with O₂ as oxidant in different solvents. Electronic spectra of the reaction mixture indicated that the oxidation proceeds through a free radical mechanism.     

Synthesis, characterization and catalytic oxidation of cyclohexene with molecular oxygen with host (nanopores of zeolite-Y)/guest (Ni(II) complexes of 14- and 16-membered tetraaza dioxo diphenyl macrocyclic ligands) nanocomposite materials

Ni(II) complexes of [14]aneN₄: 1,5,8,12-tetraaza-2,9-dioxo-4,11-diphenylcyclotetradecane; [16]aneN₄: 1,5,9,13-tetraaza-2,10-dioxo-4,12-diphenylcyclohexadecane; Bzo₂[14]aneN₄: dibenzo-1,5,8,12-tetraaza-2,9-dioxo-4,11-diphenylcyclotetradecane and Bzo₂[16]aneN₄: dibenzo-1,5,9,13-tetraaza-2,10-dioxo-4,12-diphenylcyclohexadecane have been encapsulated in the nanopores of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)nickel(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, 1,3-diaminobenzene); [Ni(N–N)₂]²⁺–NaY; in the nanopores of the zeolite-Y, and (ii) in situ condensation of the nickel(II) precursor complex with ethylcinnamate. The new host–guest nanocomposite materials (HGNM) were characterized by several techniques: chemical analysis and spectroscopic methods (FT-IR, UV/Vis, XRD and DRS) and the BET technique. These complexes were used for oxidation of cyclohexene with molecular oxygen.     

Epoxidation of cyclooctene by host (nanocavity of zeolite-Y) guest (copper(II) complexes with 16- and 17-membered diaza dioxa macrocyclic Schiff bases) nanocomposite materials

This work reports the synthesis and characterization of macrocyclic copper(II) complexes encapsulated within the nanopores of zeolite-Y. The obtained nanoparticles entrapped in the nanopores of zeolite have been characterized by FT-IR, UV–Vis, Diffuse reflectance spectra, spectroscopic techniques, molar conductance, magnetic moment data, XRD, thermal, and elemental analysis. The complexes (neat and encapsulated) were used for the oxidation of cyclooctene with tert-butyl hydroperoxide as oxidant in different solvents. The supported Cu[L₁]²⁺-Y exhibited a moderate 81.9% selectivity for epoxidation with 84.2% conversion. The catalytic activity and selectivity of the heterogeneous catalysts do not change after recycling five times.     

Template synthesis and characterization of host (nanopores of zeolite Y)/guest (Co(II)-tetraoxodithiatetraaza macrocyclic complexes) nanocomposite materials

A series of Co(II) tetraoxodithiatetraaza macrocyclic complexes ([18]aneN₄S₂, [20]aneN₄S₂, Bzo₂[18]aneN₄S₂ and Bzo₂[20]aneN₄S₂) have been encapsulated in the nanopores of zeolite Y by template condensation reaction. Co(II) complexes with tetraoxodithiatetraaza macrocyclic ligand were entrapped in the nanopores of zeolite Y by a two-steps process in the liquid phase: (i) ion-exchange of [bis(diamine)cobalt(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, 1,3-diaminobenzene); [Co(N–N)₂]²⁺–NaY; in the nano-cavity of the zeolite, and (ii) in situ template condensation of the cobalt(II) precursor complex with thiodiglycolic acid. The mode of bonding and overall geometry of the complexes and new host/guest nanocomposite materials ([Co([18]aneN₄S₂)]²⁺–NaY, [Co([20]aneN₄S₂)]²⁺–NaY, [Co(Bzo₂[18]aneN₄S₂)]²⁺–NaY, [Co(Bzo₂[20]aneN₄S₂)²⁺–NaY) has been inferred through FT-IR, DRS and UV–Vis spectroscopic techniques, BET technique, molar conductance and magnetic moment data, XRD and elemental analysis, as well as nitrogen adsorption. The average number of encapsulated Co complexes per nano-cavity was determined to be 0.33 for the Co complexes–NaY. An octahedral geometry around the cobalt(II) ion is suggested for the complexes and new host/guest nanocomposite materials.     

Host (nanocavity of zeolite-Y)/guest (12- and 14-membered azamacrocyclic Ni(II) complexes) nanocatalyst: synthesis, characterization and catalytic oxidation of cyclohexene with molecular oxygen

Ni(II) complexes of [12]aneN₄: 1,4,7,10-tetraazacyclododecane-2,3,8,9-tetraone; [14]aneN₄: 1,4,8,11-tetraazacyclotetradecane-2,3,9,10-tetraone; Bzo₂[12]aneN₄: dibenzo-1,4,7,10-tetraazacyclododecane-2,3,8,9-tetraone and Bzo₂[14]aneN₄: dibenzo-1,4,8,11-tetraazacyclotetradecane-2,3,9,10-tetraone have been encapsulated in the nanopores of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)nickel(II)]; [Ni(N–N)₂]–NaY; in the supercages of the zeolite, and (ii) in situ condensation of the nickel(II) precursor complex with diethyloxalate. The new host-guest nanocatalyst (HGN) were characterized by several techniques: chemical analysis and spectroscopic methods (FT-IR, UV/Vis, XRD, BET, DRS) and then were used for oxidation of cyclohexene with molecular oxygen.     

Host (nanopores of zeolite-Y)/guest (Ni(II)-tetraoxo dithia tetraaza macrocyclic complexes) nanocomposite materials: template synthesis and characterization

Nickel(II) complexes with six co-ordinate tetraoxo dithia tetraaza macrocyclic ligands derived from diamine and which provide a N₄S₂ co-ordination sphere, [18]aneN₄S₂: 1,4,10,13-tetraaza-5,9,14,18-tetraoxo-7,16-dithia-cyclooctadecane, [20]aneN₄S₂: 1,5,11,15-tetraaza-6,10,16,20-tetraoxo-8,18-dithia-cyclocosane, Bzo₂[18]aneN₄S₂: dibenzo-1,4,10,13-tetraaza-5,9,14,18-tetraoxo-7,16-dithia-cyclooctadecane, Bzo₂[20]aneN₄S₂: dibenzo-1,5,11,15-tetraaza-6,10,16,20-tetraoxo-8,18-dithia-cyclocosane, were entrapped in the nanopores of zeolite NaY by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)nickel(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, 1,3-diaminobenzene); [Ni(N–N)₂]²⁺-NaY; in the nanopores of the zeolite, and (ii) in situ template condensation of the nickel(II) precursor complex with thiodiglycolic acid. The mode of bonding and overall geometry of the complexes and new host/guest nanocomposite materials ([Ni([18]aneN₄S₂)]²⁺-NaY, [Ni([20]aneN₄S₂)]²⁺-NaY, [Ni(Bzo₂[18]aneN₄S₂)]²⁺-NaY, [Ni(Bzo₂[20]aneN₄S₂)²⁺-NaY) has been inferred through FT-IR, DRS and UV–vis spectroscopic techniques, molar conductance and magnetic moment data, XRD and elemental analysis, as well as nitrogen adsorption. An octahedral geometry around the nickel(II) ion is suggested for the complexes and new host/guest nanocomposite materials.     

Template synthesis and characterization of cobalt(II) complex nanoparticles entrapped in the zeolite-Y

Zeolite encapsulated complex nanoparticles “[Co([18]py₂N₄)]²⁺, [Co([20]py₂N₄)]²⁺, [Co(Bzo₂[18]py₂N₄)]²⁺ or [Co(Bzo₂[20]py₂N₄)]²⁺” were successfully prepared by the template synthesis of 2,6-diacetylpyridine with [Co(N–N)₂]²⁺ (N–N = 1,2-diaminoethane, 1,3-diaminepropane, 1,2-diaminobenzene, 1,3-diaminobenzene) within the zeolite-Y. These complex nanparticles were entrapped in the Y-zeolite by a two-step process in the liquid phase: (i) inclusion of a Co(II) precursor complex, [Co(N–N)₂]²⁺@NaY, and (ii) template synthesis of the cobalt(II) precursor complex with the 2,6-diacetylpyridine. The new complex nanoparticles entrapped in the zeolite Y “[Co([18]py₂N₄)]²⁺@NaY, [Co([20]py₂N₄)]²⁺@NaY, [Co(Bzo₂[18]py₂N₄)]²⁺@NaY, [Co(Bzo₂[20]py₂N₄)]²⁺@NaY” were characterized by several techniques: chemical analysis and spectroscopic methods (FT-IR, UV/VIS, XPS, XRD, BET, DRS). Analysis of the data indicates that the cobalt(II) complex nanoparticles are encapsulated in the zeolite-Y and exhibit different property from those of the free complexes, which can arise from distortions caused by steric effects due to the presence of sodium cations, or from interactions with the zeolite matrix.     

Syntheses,Spectroscopic, Structural,Fluorescent and Thermal Properties of Bis(saccharinato)copper(II) Complexes with two Bis(pyridylamine) Ligands

Two new copper(II) complexes of saccharinate (sac) with bis(2‐pyridylmethyl)amine (bpma) and N,N′‐bis[1‐(pyridin‐2‐yl)ethylidene]ethane‐1,2‐diamine (bapen), [Cu(bpma)(sac)₂] · H₂O ( 1 ) and [Cu(bapen)(sac)₂] ( 2 ), were synthesized and characterized by elemental analysis, TG‐DTA, X‐ray diffraction, and UV/Vis and IR spectroscopy, respectively. In 1 , the copper(II) ion is coordinated by two N‐bonded sac ligands, and three nitrogen atoms of bpma, in a distorted square‐pyramidal coordination arrangement, whereas the arrangement around the copper ion in 2 is a distorted octahedron with two N‐coordinated sac ligands and a tetradentate bapen ligand. In addition to hydrogen bonding involving the water molecule in 1 , the mononuclear species of 1 and 2 are further connected by weak intermolecular C–H ··· π and C–H ··· O interactions to form a three‐dimensional network. Both complexes are luminescent at room temperature and their emissions seem to be due to ligand‐based π–π* transitions.     

Oxovanadium(IV) and copper(II) complexes of 1,2-diaminocyclohexane based ligand encapsulated in zeolite-Y for the catalytic oxidation of styrene, cyclohexene and cyclohexane

N,N′-Bis(salicylidene)cyclohexane-1,2-diamine (H₂sal-dach) reacts with oxovanadium(IV) and copper(II) exchanged zeolite-Y in refluxing methanol to yield the corresponding zeolite-Y encapsulated metal complexes, abbreviated herein as [VO(sal-dach)]-Y and [Cu(sal-dach)]-Y. Spectroscopic studies (IR, electronic and ¹H NMR), thermal analysis, scanning electron micrographs (SEM) and X-ray diffraction patterns have been used to characterise these complexes. These encapsulated complexes catalyse the oxidation, by H₂O₂, of styrene, cyclohexene and cyclohexane efficiently in good yield. Under the optimized conditions, the oxidation of styrene catalysed by [VO(sal-dach)]-Y and [Cu(sal-dach)]-Y gave 94.6 and 21.7% conversion, respectively, where styreneoxide, benzaldehyde, benzoic acid, 1-phenylethane-1,2-diol and phenylacetaldehyde being the major products. Oxidation of cyclohexene catalysed by these complexes gave cyclohexeneoxide, 2-cyclohexene-1-ol, cyclohexane-1,2-diol and 2-cyclohexene-1-one as major products. Conversion of cyclohexene achieved was 86.6% with [VO(sal-dach)]-Y and 18.1% with [Cu(sal-dach)]-Y. A maximum of 78.1% conversion of cyclohexane catalysed by [Cu(sal-dach)]-Y and only 21.0% conversion by [VO(sal-dach)]-Y with major reaction products of cyclohexanone, cyclohexanol and cyclohexane-1,2-diol have been obtained.     

Template synthesis and characterization of diaza dioxa macrocyclic nanosized cobalt(II) complex dispersed within nanocavity of zeolite-Y

Nanocavity microreactor containing 15- and 16-membered diaza dioxa Schiff-base cobalt(II) complexes “[Co(Et[15]N₂O₂)]²⁺, [Co(Pr[16]N₂O₂)]²⁺, [Co(Ph[15]N₂O₂)]²⁺ and [Co(Ch[15]N₂O₂)]²⁺” have been prepared by the template synthesis of diamine (1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene or 1,2-diaminocyclohexane) with [(1,3-bis(2-carboxyaldehydephenoxy)propane)cobalt]²⁺;[Co(BCAPP)]²⁺@NaY within the pores of zeolite-Y. The nanosized cobalt(II) complex were entrapped in the supercage of Y-zeolite by a three-step process in the liquid phase: (i) exchange of Co(II) ions with NaY in water solution, (ii) reaction of Co(II)–NaY with excess BCAPP in methanol; [Co(BCAPP)]²⁺@NaY; (iii) template synthesis of [Co(BCAPP)]²⁺@NaY with diamine. The new nanosized complex entrapped in the nanocavity of zeolite Y was characterized by several techniques: chemical analysis and spectroscopic methods (FT-IR, UV–Vis, XRD, BET, DRS, XPS, TGA).     

NHC–Pd(II) complex–Cu(I) co‐catalyzed homocoupling reaction of terminal alkynes

Two NHC–Pd(II) complexes synthesized from trans‐cyclohexane‐1,2‐diamine were fairly effective in the NHC–Pd(II) complex/Cu co‐catalyzed terminal alkyne homocoupling reaction to give the corresponding symmetrical 1,4‐disubstituted 1,3‐diynes in good yields under mild conditions. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis,Characterization and Solvatochromism Investigation of Mixed Ligand Chelate Copper(II) Complexes with Acetyleacetonate and Three Diamine Ligands

The syntheses of three mixed ligand chelate copper(II) complexes of the type [Cu(L)(acac)(H₂O)]BPh₄ where acac=acetyleacetonate; L=N,N‐dimethyl,N′‐benzylethane‐1,2‐diamine ( L¹ ), N,N‐dimethyl, N′‐2‐methylbenzylethane‐1,2‐diamine ( L² ) or N,N‐dimethyl,N′‐2‐chlorobenzylethane‐1,2‐diamine ( L³ ) are reported and characterized by elemental analyses, spectroscopic and molar conductance measurements. The X‐ray structure of complex 1 shows that the central copper atom is placed in a distorted square pyramidal geometry made by acac and diamine chelate in the base and a H₂O molecule on the apex. The prepared complexes are fairly soluble in a large number of organic solvents and show positive solvatochromism. Calculations of SMLR (stepwise multiple linear regression) method was utilized to find the best model explaining the observed solvatochromic behavior and showed that among different solvent parameters, donor number (DN) is a dominant factor responsible for the shift in the d‐d absorption band of the complexes to the lower wavenumber with increasing its values. The importance of substituent effect in diamine ligand on the spectral and SMLR measurements is also discussed.     

Synthesis,characterization and catalytic oxidation of cyclohexene with molecular oxygen over host (nanopores of zeolite-Y)/guest ([Ni([R]2-N2X2)]2+ (R = H,CH3; X = NH,O, S) nanocatalyst

Nickel(II) complexes of 12-membered macrocyclic ligands with different donating atoms (N₂O₂, N₂S₂ and N₄) in the macrocyclic ring have been encapsulated in the nanocavity of zeolite-Y by the fexible-ligand method. Nickel(II) complexes with macrocyclic ligands were entrapped in the nanocavity of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of precursor ligand; 1,2-di(o-aminophenyl-, amino, oxo, thio)ethane, N₂X₂; in the supercages of the Ni(II)–NaY, and (ii) in situ condensation of the Ni(II) precursor complex; [Ni(N₂X₂)]²⁺; with glyoxal or biacetyl. The new host–guest nanocatalysts (HGNM), [Ni([R]₂-N₂X₂)]²⁺–NaY (R = H, CH₃; X = NH, O, S), have been characterized by FT-IR, DRS and UV–Vis spectroscopic techniques, XRD and elemental analysis, as well as nitrogen adsorption, and were used for oxidation of cyclohexene with molecular oxygen.     

Synthesis, characterization, biological and thermal studies of Cu(II) complexes of salen and tetrahedrosalen ligands

A series of mononuclear salen type copper(II) complexes, [CuLⁿ] (n = 1–4), and their corresponding tetrahydrosalen complexes, [CuH₂Lⁿ] (n = 1,2) were prepared by the reaction of the N₂O₂ ligands with Cu(II) ion in ethanol, where H₂L¹ = N,N-bis(3,5-di-tert-butylsalicylidene)-2,2-dimethyle-1,3-diaminopropan, H₂L² = N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminopropane, H₂L³ = N,N-bis(4-methoxysalicylidene)-2,2-dimethyle-1,3-diaminopropan; H₂L⁴ = N,N-bis(4-methoxysalicylidene)-1,2-diaminopropane, H₂[H₂L¹] = N,N-bis(2-hydroxyl-3,5-di-tert-butylphenyl)-2,2-dimethyle-1,3-diaminopropan and H₂[H₂L²] = N,N-bis(2-hydroxyl-3,5-di-tert-butylphenyl)-1,2-diaminopropane. The prepared ligands and complexes were characterized by the combination of IR, UV-Vis, NMR (as far as possible), elemental and thermal analyses. All prepared compounds were also evaluated for their antibacterial (Escherichia coli and Staphylococcus aureus) and antifungal (Candida albicans) activities by the disc diffusion method. The compounds were found have no remarkable antimicrobial activities.     

Synthesis, spectral and electrochemical studies of Cu(II) and Ni(II) complexes with new N2O2 ligands: a new precursor capable of depositing copper nanoparticles using thermal reduction

Cu(II) and Ni(II) complexes of the general type [M(N2O2)] are described. The N2O2 ligands used are [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,3-diamine] (HOMeSalpn) and [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,2-diamine (HOMeSalpr). These complexes have been characterized by IR, UV-vis, CV, TG-DTA and 1H NMR spectroscopy. The electrochemical behavior of these complexes at a glassy carbon electrode in acetonitrile solution indicates that the first reduction process corresponding to Cu(II)-Cu(I) and Ni(II)-Ni(I) is electrochemically irreversible. The new copper complexes have been applied for the preparation of copper nanoparticles using non-ionic surfactant (Triton X-100) by thermal reduction. The copper nanoparticles with average size of 48nm were formed by thermal reduction of [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,3-diamine]copper(II) in the presence of triphenylphosphine thus releasing the reduced copper and affording the high-purity copper nanoparticles.     

Syntheses and X‐ray Structure Analyses of the First Bis(chelated) Copper and Iron Bisguanidine Complexes

The synthesis of N¹,N²‐bis(1,3‐dimethylimidazolidin‐2‐ylidene)ethane‐1,2‐diamine and the synthesis and structure determination of bis{N¹,N²‐bis(1,3‐dimethylimidazolidin‐2‐ylidene)ethane‐1,2‐diamine}copper(II)‐tetraiododicuprate(I) ([Cu(DMEG₂e)₂][Cu₂I₄]) and bis{N¹,N²‐bis(1,3‐dimethylimidazolidin‐2‐ylidene)ethane‐1,2‐diamine}iron(II)‐octacarbonyl‐diferrate(‐I) ([Fe(DMEG₂e)₂][Fe₂(CO)₈]) which represent the first bis(chelated) bisguanidine complexes are described. The dicationic [M(DMEG₂e)₂]²⁺ molecules with M = Cu, Fe follow the same structural principles and thus differ in their coordination geometries from ideal‐typical expectations.     

Synthesis and characterization of 18- and 20-membered hexaaza macrocycles containing pyridine manganese(II) complex nanoparticles dispersed within nanoreactors of zeolite-Y

Manganese(II) complexes of [18]py₂N₄: 3,6,14,17,23,24-hexaazatricyclo[17.3.1.1^8,12]tetracosa-1(23),2,6,8(24),9,11,13,17,19,21-decane; [20]py₂N₄: 3,7,15,19,25,26-hexaazatricyclo[19.3.1.1^9,13]hexacosa-1(25),2,7,9(26),10,12,14,19,21,23-decaene; Bzo₂[18]py₂N₄: 3,10,18,25,31,32-hexaazapentacyclo[25.3.1.1.^12,16.0^4,9.0^19,24]dotriaconta 1(31),2,4(9),5,7,10,12(32),13,15,17,19,21,23,25,29-hexadecane and Bzo₂[18]py₂N₄: 2,10,16,24,30,32-hexaazapentacyclo[23.3.1.1^4,8.1^1,1,151^18,22otriaconta-1(29),2,4,6,8(32),9,11,13,15(31),16,18(30),19,21,23,25,27-hexadecane have been encapsulated in the nanopores of zeolite-Y by the template condensation reaction. Mn(II) complexes with macrocyclic ligand were entrapped in the nanocavity of zeolite-Y by a two-step process in the liquid phase: (i) the adsorption of [bis(diamine)manganese(II)]; [Mn(diamine)₂]²⁺@NaY; in the supercages of the zeolite, and (ii) in situ condensation of the manganese(II) precursor complex with 2,6-diacetylpyridine. The new complex nanoparticles entrapped in the nanoreactor of zeolite-Y have been characterized by FT-IR, diffuse reflectance (DRS), X-ray photoelectron (XPS), thermal analysis, UV–Vis spectroscopic techniques, X-ray diffraction (XRD) and elemental analysis as well as by nitrogen adsorption.     

Copper(II) complexes with derivatives of salen and tetrahydrosalen: a spectroscopic, electrochemical and structural study

Salen type complexes, CuL, the corresponding tetrahydrosalen type complexes, Cu[H₄]L, and N,N′-dimethylated tetrahydrosalen type complexes, Cu[H₂Me₂]L, were investigated using cyclic voltammetry, and electronic and ESR spectroscopy. In addition, the analogous copper(II) complexes with a derivative of the tetradentate ligand ‘salphen’ [salphen=H₂salphen=N,N′-disalicylidene-1,2-diaminobenzene] were studied. Solutions of CuL, Cu[H₄]L and Cu[H₂Me₂]L are air-stable at ambient temperature, except for the complex Cu(^tBu, Me)[H₄]salphen [H₂(^tBu, Me)[H₄]salphen=N,N′-bis(2-hydroxy-3-tert-butyl-5-methylbenzyl)-1,2-diaminobenzene]. Cu(^tBu, Me)[H₄]salphen interacts with dioxygen and the ligand is oxidatively dehydrogenated (–CH₂–NH–→–C=N–) to form Cu(^tBu, Me)[H₂]salphen and finally, in the presence of base, Cu(^tBu, Me)salphen. X-ray structure analysis of Cu(^tBu, Me)[H₂Me₂]salen confirms a slightly tetrahedrally distorted planar geometry of the CuN₂O₂ coordination core. The complexes were subjected to spectrophotometric titration with pyridine, to determine the equilibrium constants for adduct formation. It was found that the metal center in the complexes studied is only of weak Lewis acidity. In dichlormethane, the oxidation Cu(II)/Cu(III) is quasireversible for the CuL type complexes, but irreversible for the Cu[H₄]L and Cu[H₂Me₂]L type. A poorly defined wave was observed for the irreversible reduction Cu(II)/Cu(I) at potentials less than −1.0 V. The ESR spectra of CuL at both 77 K and room temperature reveal that very well resolved lines can be attributed to the interaction of an unpaired electron spin with the copper nuclear spin, ¹⁴N donor nuclei and to a distant interaction with two equivalent protons [A^Cu(iso)≈253 MHz, A^N(iso)≈43 MHz, A^N(iso)≈20 MHz]. These protons are attached to the carbon atoms adjacent to the ¹⁴N nuclei. In contrast to CuL, the number of lines in the spectra of the complexes Cu[H₄]L and Cu[H₂Me₂]L is greatly reduced. At room temperature, only a quintet with a considerably smaller nitrogen shf splitting constant [A^N(iso)≈27 MHz] is observed. Both factors, planarity and conjugation, are thus essential for the observation of distant hydrogen shf splitting in CuL. Due to the C=N bond hydrogenation, the coordination polyhedra of the complexes Cu[H₄]L and Cu[H₂Me₂]L is more flexible and more sensitive to ligand modification than that of CuL. The electron-withdrawing effect of the phenyl ring of the phenylenediamine bridge is reflected in a reduction of the copper hyperfine coupling constants in Cu(^tBu, Me)[H₄]salphen and Cu(^tBu, Me)[H₂Me₂]salphen complexes [A^Cu(iso)≈215 MHz].     

Syntheses,Characterization and Crystal Structures of Three Structurally Similar Dinuclear Schiff Base Cadmium(II) Complexes with Bridging Azide or Thiocyanate Ligands

Three novel Schiff base cadmium(II) complexes, derived from the end‐on (μ‐1,1‐N₃) azide or end‐to‐end (μ‐1,3‐NCS) thio cyanate bridges and similar tridentate Schiff base ligands, have been synthesized under similar synthetic procedures and their crystal structures determined by X‐ray diffraction methods. They are the dinuclear double end‐on azide‐bridged [Cd₂(L1)₂(N₃)₂(μ‐1,1‐N₃)₂] ( 1 ), the dinuclear double end‐on azide‐bridged [Cd₂(L2)₂(N₃)₂(μ‐1,1‐N₃)₂] ( 2 ), and the dinuclear double end‐to‐end thiocyanate‐bridged [Cd₂(L3)₂(NCS)₂(μ_1,3‐NCS)₂] ( 3 ), where L1, L2 and L3 are three similar tridentate Schiff bases obtained by condensation of 2‐pyridylaldehyde with N,N‐diethylethane‐1,2‐diamine, of 2‐pyridylaldehyde with N‐isopropylethane‐1,2‐diamine, and of 2‐pyridylaldehyde with N,N‐dimethylpropane‐1,3‐diamine, respectively. Each cadmium(II) centre in the complexes is in a distorted octahedral coordination. There is a crystallographic inversion centre in each of the complexes. The similar small ligands used as the secondary ligands in the preparation of the cadmium(II) complexes with similar Schiff bases can result in similar structures.     

Synthesis,Crystal Structures,and Urease Inhibitory Activities of Three Novel Thiocyanato‐bridged Polynuclear Schiff Base Cadmium(II) Complexes

Three novel thiocyanato‐bridged polynuclear cadmium(II) complexes, [Cd(HL1)(NCS)₂(μ_1,3‐NCS)]_n ( 1 ), [CdL2(μ_1,3‐NCS)₂]_n ( 2 ), and [CdL3(μ_1,3‐NCS)₂]_n ( 3 ) (L1 = N‐methyl‐N′‐(1‐pyridin‐2‐ylmethylidene)ethane‐1,2‐diamine, L2 = 2‐(cyclopropyliminomethyl)‐6‐methoxyphenol, L3 = 2‐(cyclopentyliminomethyl)‐6‐methoxyphenol), have been synthesized and structurally characterized by elemental analysis, IR spectra and single‐crystal X‐ray diffraction. Each cadmium(II) atom in the complexes is in an octahedral coordination. The urease inhibitory activities of the complexes were evaluated. All of them showed potent inhibitions against jack bean urease.