Copper(II) complexes as catalyst for the aerobic oxidation of o-phenylenediamine to 2,3-diaminophenazine.

Two new mononuclear copper(II) complexes [Cu (L) (NO3)2] (1) and [Cu (L) Br2] (2) where (L=bis(1-(pyridin-2-ylmethyl)-benzimidazol-2-ylmethyl)ether) are synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, UV-Visible, IR spectroscopy, EPR and cyclic voltammetry. The complexes exhibit different coordination structures; the E1/2 value of the complex (1) is found to be relatively more cathodic than that of complex (2). X-band EPR spectra at low temperature in DMF supports a tetragonally distorted complex (1) while complex (2) shows three different g values suggesting a rhombic geometry. These complexes were utilized as a catalyst for the aerobic oxidation of o-phenylenediamine to 2,3-diaminophenazine assisted by molecular oxygen. The initial rate of reaction is dependent on the concentration of Cu(II) complex as well as substrate, and was found to be higher for the nitrate bound complex, while presence of acetate anion acts as a mild inhibitor of the reaction, as it is likely to pick up protons generated during the course of reaction. The inhibition suggests that the generated protons are further required in another important catalytic step.

Oxidation of phenyl propyne catalyzed by copper(II) complexes of a benzimidazolyl schiff base ligand: effect of acid/base, oxidant, surfactant and morphology.

Copper(II) complexes with a new N-Substituted benzimidazolyl schiff base ligand are used as catalyst for the oxidation of 1-phenyl propyne. The oxidation is carried out under mild conditions using stoichiometric amounts of oxidant and catalytic amounts of Cu(II) complex as catalyst. Effect of acid/base, oxidant, morphology and surfactant has been studied. Two major products of phenyl propyne oxidation are the α-diketonic product and a terminal aldehyde. Diketone is the major product under acidic conditions while aldehyde formation is highest under basic conditions. The maximum conversion is found with the NO3(-) bound complex. GC-MS is used to find the percentage yields of products. SEM and PXRD of the reused complexes as catalyst suggest that morphology affects the catalytic efficiency.

Oxidation of substituted phenols using copper(II) metallatriangles formed through ligand sharing.

Reaction of N(2),N(2')-bis-[(1-butyl-benzimidazol-2yl)methyl]biphenyl-2,2'-dicarboxamide (L) with CuX2⋅nH2O in methanol leads to the assembly of four trinuclear Cu(II) complexes with the general formula [Cu3(L)3X3]⋅3X⋅nH2O⋅mMeCN, where X=Cl(-), Br(-), NO3(-) and C6H5COO(-) and n=0-5, m=0-8 (compounds 1-4, respectively). The structure of one of the complex contains three Cu(II) metal ions at the corners of an equilateral triangle. Each of the copper(II) are coordinated through two benzimidazolyl imine N-atoms and two amide carbonyl O-atoms and the apical position is occupied by an anionic nitrate ion, leading to a distorted square pyramidal environment. The magnetic susceptibility data were analyzed through Hamiltonian H=-J (S1S2+S2S3+S1S3) obtaining -J=0.16, 0.12, 0.15 and 0.14cm(-1) for 1-4, respectively. X-Band EPR spectra typically show a broad single line at 120K with g∼2.11. Oxidation of phenols was studied homogeneously using copper(II) metallatriangles (1-3) as catalyst in acetonitrile. The oxidation of 2,4,6-tri-tert-butyl phenol yields the corresponding quinone after oxidative dealkylation. The oxidation of 2-amino-5-methyl phenol yields the corresponding phenoxazinone while the oxidation of 2-amino-4-tert-butyl phenol yields the phenoxazine instead of phenoxazinone. The products so obtained were analyzed by NMR and X-ray single crystallography.

Synthesis of a new N-substituted bis-benzimidazolyl diamide ligand and its trinuclear copper(II) complex: structural and fluorescence studies.

The synthesis of a new N-substituted fluorescent probe based on a bis-benzimidazole diamide N(2),N(2')-bis[(1-(4-methylbenzyl)-benzimidazol-2-yl)methyl]biphenyl-2,2'-dicarboxamide (L1) with a biphenyl spacer group and its trinuclear copper(II) complex [Cu3(L1)3Cl3]·3Cl·3H2O] has been described. X-ray studies shows that the trinuclear complex crystallizes as [{Cu3(L1)3Cl3}2·6Cl·13CH3CN·2H2O] in triclinic space group P-1 with two independent molecules in the asymmetric unit. Each copper(II) adopts a distorted penta-coordinated geometry in each unit. The fluorescence spectra of L1 in methanol show an emission band centered at 300 nm. This band arises due to benzimidazolyl moiety in the ligating system. The diamide L1 in the presence of Fe(3+) show the simultaneous 'quenching' of (300nm) and 'enhancement' of (375 nm) emission band. The new emission band at 375 nm is attributed to intra ligand π-π(*) transition of the biphenyl moiety. While Cu(2+) and Ag(+) show only the quenching of the 300 nm band. No such behavior was observed with other metal ions like Ni(2+), Co(2+), Mn(2+), Mg(2+), Zn(2+) and Pb(2+). The quenching constant with Fe(3+), Ag(+) and Cu(2+) are calculated by the Stern-Volmer plots.

Dimeric copper(II) complex of a new Schiff base ligand: effect of morphology on the catalytic oxidation of aromatic alcohol.

An antiferromagnetically coupled, dimeric µ-naphthanoxo bridged copper(II) complex is used heterogeneously to catalyze oxidation of p-chlorobenzylalcohol to aldehyde selectively. PL and PXRD studies reveal that during recycling the catalyst remains essentially intact. However loss of catalytic efficiency upon reuse is in consonance with a loss in morphology as indicated by SEM.

Bis-benzimidazolyl diamide based fluorescent probe for copper(II): synthesis, structural and fluorescence studies.

A new fluorescent probe based on a bis-benzimidazole diamide N (2),N (2')-bis[(1-ethyl-benzimidazol-2-yl)methyl]biphenyl-2,2'-dicarboxamide ligand L 1 with a biphenyl spacer group and a Copper(II) trinuclear metallacycle has been synthesized and characterized by X-ray single crystallography, elemental and spectral (FT-IR, (1)H & (13)C NMR, UV-Visible) analysis. The fluorescence spectra of L 1 in MeOH show an emission band centered at 300 nm. This band arises due to benzimidazolyl moiety in the ligating system. The diamide L 1 in the presence of Cu(2+) show the simultaneous 'quenching' of (300 nm) and 'enhancement' of (375 nm) emission band. Similar fluorescence behavior was found in water-methanol mixture (9:1). The new emission band at 375 nm is attributed to intra ligand π-π* transition of the biphenyl moiety. L 1 exhibited high selectivity and sensitivity towards Cu(2+) in both the medium over other common metal ions like Ni(2+), Co(2+), Mn(2+), Mg(2+), Zn(2+), Pb(2+) and Hg(2+). The binding constant with Cu(2+) was calculated by the Benesi-Hildebrand equation. Selective "off-on-off" behavior of L 1 in methanol has also been studied. The fluorescent intensity of 375 nm bands in L 1 enhances (turns-on) upon addition of Cu(2+) and quenches (turn-off) upon addition of Na2-EDTA.

Iron(III) complexes of bis (benzimidazol-2-yl) methyl) thiophene-2,5-dicarboxamide: synthesis, spectral and oxidation of o-phenylenediamine.

Iron(III) complexes of a potentially pentadentate ligand N(2), N(5)-bis ((1H-benzo [d] imidazol-2-yl) methyl) thiophene-2,5-dicarboxamide are synthesized with an exogenous anion X=Cl(-), NO(3)(-). Mössbauer and EPR spectroscopy indicates axially distorted complexes. These complexes were utilized for the oxidation of o-phenylenediamine to 2,3-diaminophenazine in presence of H(2)O(2). The initial rate of reaction is dependent on the concentration of o-phenylenediamine as well as the iron(III) complex. Rates of reaction were found to be at least five times higher for the Cl(-) bound complex. The effect of an added anion like acetate, azide and citrate is found to inhibit the rate of reaction. This suggests that one of the factors affecting the rate determining step is the binding of these anions on a vacant site at the iron(III) centre. The oxidation of o-phenylenediamine to 2,3-diaminophenazine is reminiscent of the functioning of horse radish peroxidase.

Fe (III) complexes of a bis-benzimidazolyl diamide ligand: spectral and catalytic studies.

A new tetradentate bis benzimidaozlyl diamide ligand N,N'-Bis (benzimidazol-2-yl-methyl)-hexane-1,6-dicarboxamide (GBSA) has been synthesized and utilized to prepare new Fe(III) complexes with exogenous anionic ligand X=Cl(-) and NO(3)(-). Isomer shift values are in the range found for Iron in the +3 oxidation state while Quadrupole Splitting indicates large distortion from a six coordinate geometry, a finding supported by low temperature EPR work. The E(1/2) values are found to be quite cathodic indicating stability of the Iron (III) complexes. The oxidation of alcohols was investigated using [Fe(GBSA)Cl(3)] as the catalyst with TBHP as an alternate source of oxygen. The respective carbonyl products have been isolated and characterized by (1)H NMR, electronic spectroscopy, mass and IR spectral studies.

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

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

Synthesis and spectral studies of copper complexes using a N-octylated bis benzimidazole diamide ligand.

Monomeric Cu(II) and Cu(I) complexes bound to a tetradentate bis-benzimidazole diamide ligand N,N'-bis(N-octyl benzimidazolyl-2yl)(methyl)pentane diamide (O-GBGA) have been isolated and characterized. X-Band EPR spectra of the copper(II) complexes in CH2Cl2 were recorded in a frozen solution as solvent at liquid nitrogen temperature. Solution spectra typically indicate a d(x2-y2) ground state (g||>g⊥>2.0023) and show less than four nuclear hyperfine lines with broadening of g⊥ line in some cases, thus indicating distorted tetragonal geometry. One of the copper(II) complexes shows a five line N-SHF structure (16±1G) implying the binding of imine nitrogen of the benzimidazole to copper ion. α2 ranges from 0.57-0.97 indicating considerable amount of covalent character in Cu-L bond. Anodic shifts in E1/2 values indicate the retention of anion in the coordination sphere of Cu(II), E1/2 values becoming anodic in the order C6H5COO-

Oxidation of alcohols using a manganese (II) complex based on a pentakis benzimidazole amide ligand.

A pentakis benzimidazole based penta-amide ligand diethylenetriamine-N,N,N',N',N''-pentakis(2-methyl benzimidazolyl)penta-amide [GBDTPA] has been synthesized and utilized to prepare Mn (II) complexes of general composition [Mn(2)(GBDTPA)X(4)], where X is an exogenous anionic ligand (X = Cl(-), NO(3)(-) and Br(-)). The oxidation of alcohols has been investigated using [Mn(2)(GBDTPA)Cl(4)] as the catalyst and TBHP as an alternate source of oxygen. The respective aldehydic products have been isolated and characterized by (1)H NMR.

Synthesis, spectral and oxidase studies of a new diamide copper(II) complex with pendant benzimidazolyl groups.

A new benzimidazole-based diamide ligand-N,N'-bis(alanine-2-benzimidazolyl) hexanediamide (ABHA) has been synthesized and utilized to prepare Cu(II) complexes of general composition [Cu(ABHA)X2].nH2O,where X is an exogenous anionic ligand (X=Cl-,NO3-). Low temperature EPR spectra has been obtained that shows gparallel>gperpendicular>2.0024, indicating a tetragonal geometry in the solution state. The complexes display a quasi-reversible redox wave due to the Cu(II)/Cu(I) reduction process. E1/2 values shift anodically as NO3-

Copper(II) complexes of N-octylated bis(benzimidazole) diamide ligands and their peroxide-dependent oxidation of aryl alcohols.

New N-octylated benzimidazole-based diamide ligands N,N'-bis(N-octylbenzimidazolyl-2-ethyl)hexanediamide (O-ABHA), possessing a chiral center, and N,N'-bis(N-octylbenzimidazolyl-2-methyl)hexanediamide (O-GBHA) have been synthesized and utilized to prepare Cu(II) complexes of general composition [Cu(L)X]X, where L = O-ABHA or O-GBHA and X = Cl(-) or NO(3)(-) . The X-ray structure of one of the complexes, [Cu(O-GBHA)NO(3)]NO(3), has been obtained. The Cu(II) ion is found to possess a distorted octahedral geometry with a highly unsymmetrical bidentate nitrate group. The N(2)O(2) equatorial plane comprises an amide carbonyl O, a nitrate O, and the two benzimidazole imine N atoms while another amide carbonyl O and nitrate O take up the axial positions. The complexes carry out the oxidation of aromatic alcohols to aldehydes in the presence of cumenyl hydroperoxide at 40-45 degrees C and act as catalyst with turnovers varying between 13- and 27-fold. The percentage yields of the respective products have been obtained which vary from 32% to 65% with respect to the catalyst turnover.