Targeted water soluble copper-tetrazolate complexes: interactions with biomolecules and catecholase like activities.

Two new mononuclear water soluble copper(II) complexes, [Cu{(5-pyrazinyl)tetrazolate}2(1,10-phenanthroline)] 1 and [Cu{(5-pyrazinyl)tetrazolate}(1,10-phenanthroline)2](NO3)0.5(N3)0.5 2, have been synthesized using the metal mediated [2 + 3] cycloaddition reaction between copper bound azide and pyrazinecarbonitrile. The interactions of these copper tetrazolate complexes 1 and 2 with biomolecules like DNA and bovine serum albumin (BSA) are studied and the catecholase like catalytic activity of compound 2 is also explored. Structural determination reveals that both compounds 1 and 2 are octahedral in nature. Screening tests were conducted to quantify the binding ability of complexes (1 and 2) towards DNA and it was revealed that complex 2 has a stronger affinity to bind to CT-DNA. DFT studies indicated that a lower HOMO-LUMO energy gap between the DNA fragment and metal complexes might be the reason for this type of stronger interaction. DNA cleavage activity was explored by gel-electrophoresis and moderate to strong DNA cleavage properties were observed in the presence and absence of co-reagents. Inhibition of cleavage in the presence of sodium azide indicates the propagation of the activity through the production of singlet molecular oxygen. Furthermore enzyme kinetic studies reflect that complex 2 is also effective in mimicking catecholase like activities. An ESI-MS spectral study indicates the probable involvement of dimeric species [(phen)2Cu-(OH)2-Cu(phen)2](2+) in the catalytic cycle.

Greener Selective Cycloalkane Oxidations with Hydrogen Peroxide Catalyzed by Copper-5-(4-pyridyl)tetrazolate Metal-Organic Frameworks.

Microwave assisted synthesis of the Cu(I) compound [Cu(µ4-4-ptz)]n [1, 4-ptz=5-(4-pyridyl)tetrazolate] has been performed by employing a relatively easy method and within a shorter period of time compared to its sister compounds. The syntheses of the Cu(II) compounds [Cu3(µ3-4-ptz)4(µ2-N3)2(DMF)2]n∙(DMF)2n (2) and [Cu(µ2-4-ptz)2(H2O)2]n (3) using a similar method were reported previously by us. MOFs 1-3 revealed high catalytic activity toward oxidation of cyclic alkanes (cyclopentane, -hexane and -octane) with aqueous hydrogen peroxide, under very mild conditions (at room temperature), without any added solvent or additive. The most efficient system (2/H2O2) showed, for the oxidation of cyclohexane, a turnover number (TON) of 396 (TOF of 40 h(-1)), with an overall product yield (cyclohexanol and cyclohexanone) of 40% relative to the substrate. Moreover, the heterogeneous catalytic systems 1-3 allowed an easy catalyst recovery and reuse, at least for four consecutive cycles, maintaining ca. 90% of the initial high activity and concomitant high selectivity.

Nickel(II) complexes with a flexible piperazinyl moiety: studies on DNA and protein binding and catecholase like properties.

Four new mononuclear Ni(ii) complexes [Ni(L(1))]ClO4 (), [Ni(L(2))]ClO4(), [Ni(SCN)3(CH3OH)(aminoethylpiperazineH)] (), and [Ni(DMSO)4(aminoethylpiperazineH)](ClO4)3()have been synthesized from two Schiff base ligands [L(1) = 1-phenyl-3-((2-(piperidin-4-yl)ethyl)imino)but-1-en-1-ol and L(2) = 4-((2-(piperazin-1-yl)ethyl)imino)pent-2-en-2-ol] by exploiting the flexibility of the piperazinyl moiety. Structural analysis reveals that and are square planar complexes with piperazine rings in boat conformations whereas hydrolysis of Schiff bases (L(1) and L(2)) occurs during formation of octahedral complexes ( and ) with piperazine rings in chair conformations. Screening tests were conducted to quantify the binding ability of complexes (, and ) towards DNA, BSA and HSA and it was found that square planar complexes ( and ) showed more effective binding properties over octahedral complex (). Furthermore, enzyme kinetic studies reflect that square planar complexes ( and ) are also effective in mimicking catecholase like activities over octahedral complex (). Among all the complexes, was found to be the most promising molecule among the series due to its large binding affinity towards different bio-macromolecules and higher T.O.N in the catechol oxidation reaction.

Copper-organic frameworks assembled from in situ generated 5-(4-pyridyl)tetrazole building blocks: synthesis, structural features, topological analysis and catalytic oxidation of alcohols.

Two new metal-organic compounds {[Cu3(µ3-4-ptz)4(µ2-N3)2(DMF)2](DMF)2}n (1) and {[Cu(4-ptz)2(H2O)2]}n (2) {4-ptz = 5-(4-pyridyl)tetrazolate} with 3D and 2D coordination networks, respectively, have been synthesized while studying the effect of reaction conditions on the coordination modes of 4-pytz by employing the [2 + 3] cycloaddition as a tool for generating in situ the 5-substituted tetrazole ligands from 4-pyridinecarbonitrile and NaN3 in the presence of a copper(ii) salt. The obtained compounds have been structurally characterized and the topological analysis of 1 discloses a topologically unique trinodal 3,5,6-connected 3D network which, upon further simplification, results in a uninodal 8-connected underlying net with the bcu (body centred cubic) topology driven by the [Cu3(µ2-N3)2] cluster nodes and µ3-4-ptz linkers. In contrast, the 2D metal-organic network in 2 has been classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology assembled from the Cu nodes and µ2-4-ptz linkers. The catalytic investigations disclosed that 1 and 2 act as active catalyst precursors towards the microwave-assisted homogeneous oxidation of secondary alcohols (1-phenylethanol, cyclohexanol, 2-hexanol, 3-hexanol, 2-octanol and 3-octanol) with tert-butylhydroperoxide, leading to the yields of the corresponding ketones up to 86% (TOF = 430 h(-1)) and 58% (TOF = 290 h(-1)) in the oxidation of 1-phenylethanol and cyclohexanol, respectively, after 1 h under low power (10 W) microwave irradiation, and in the absence of any added solvent or additive.

Limiting nuclearity in formation of polynuclear metal complexes through [2 + 3] cycloaddition: synthesis and magnetic properties of tri- and pentanuclear metal complexes.

A tridentate ligand p-chloro-2-{(2-(dimethylamino)ethylimino)methyl}phenol (HL) was used to generate an octahedral nickel complex [Ni(L)Cl(H2O)2] 1 which was further converted into a square-planar nickel complex [Ni(L)(N3)] 2. The [2 + 3] cycloaddition reaction between metal coordinated azide 2 and different organonitriles under microwave irradiation afforded tri- and pentanuclear nickel(II) complexes 4a-4c. Reaction with benzonitrile and 3-cyano pyridine furnished the trinuclear species [Ni3L2(5-phenyltetrazolato)4(DMF)2] 4a and [Ni3L2{5-(3-pyridyl)-tetrazolato}4(DMF)2]·2H2O 4b, respectively. The nickel centers were found to be linearly disposed to each other and the complex is formed by a 2,3-tetrazolate bridge and a phenoxo bridge between central and terminal nickel atoms. Compound 2 when treated with 1,2-dicyanobenzene under identical conditions furnished a pentanuclear complex [Ni5L4{5-(2-cyanophenyl)-tetrazolato}4(OH)2(H2O)2]·3H2O·DMF 4c. In this pentanuclear compound two dimeric nickel units are connected to the central nickel center by a µ3-hydroxo bridge and a tetrazolate ligand operating via a relatively rare 1,2,3-bridging mode. The compounds were characterized by IR, elemental analysis, thermogravimetric analysis and single crystal X-ray crystallography. The magnetic susceptibility data for compounds 4a-4c show dominant antiferromagnetic interactions between the nickel centers for all the complexes. DFT calculations were performed to investigate the magnetic parameter in one of the complexes 4b by a broken symmetry approach.