Transition Metal Perchlorates Research Articles

Tailoring Transition Metals and Biuret into Laser-Ignitable Energetic Coordination Polymers with Improved Oxygen Balance and Multidentate Coordination Structures

Eight kinds of energetic coordination polymers (ECPs) with multi-coordination were designed and synthesized by combining the carbonyl group with coordination potential in biuret with transition metal nitrates and perchlorates (Co2+, Ni2+, Cu2+, and Ag+). The structures of these complexes are confirmed by infrared spectroscopy, elemental analysis, and X-ray single-crystal diffraction. The physical and chemical performance test results show that the solvent-free ECPs 7 (Cu(BIU)2(ClO4)2) has the best performance (Tdec = 328 °C, D = 7600 km·s–1, P = 27.8 Gpa, IS = 25 J, FS = 240 N). Among them, ECPs 7 and 8 (Ag(BIU)ClO4) have good detonation performance during hot plate and laser ignition tests (ECPs 7: P = 15 W, τ = 6 ms, E = 80 mJ; ECPs 8: P = 20 W, τ = 5 ms, E = 100 mJ). The result shows that improving the oxygen balance of ligands and constructing multidentate coordination structures may be a new effective strategy for improving the performance of laser-sensitive ECPs.

Coordination polymers of a dipyridylazacrown ligand: structural, thermal and spectroscopic properties

Treatment of the dipyridylazacrown ether ligand N,N′-bis(4-pyridyl-methyl)diaza-18-crown-6 (bpmdc), with hydrated transition metal perchlorate salts resulted in 2D networks with the composition [M(H2O)2(Hbpmdc)2](ClO4)4·xH2O (M2+ = Ni, x = 4 (1); Cu, x = 2 (2) and Zn, x = 4 (3)). The addition of sodium thiocyanate led to displacement of the aqua ligands, yielding [M(NCS)2(Hbpmdc)2](ClO4)2·2H2O (M2+ = Fe (4), Ni (5)), as well as a THF containing variant of Fe (6). A five-coordinate, copper-containing 2D network, [Cu(NCS)(bpmdc)2](NCS) (7), was isolated in the case of copper, while zinc proved to be the exception to the 2D coordination polymer motif, yielding a 1D chain motif [Zn(NCS)2(bpmdc)2] (8). Across these structures the dipyridylazacrown ether ligand showed a remarkably consistent adoption of the S-configuration when empty or singly protonated with a water guest, with bridging lengths varying by only 1.3 A. The magnetic behaviour of the Fe2+ network 4 was investigated and the d6 compound was found to remain high spin at all temperatures between 300 and 2 K, and thus did not show spin-crossover behaviour.

Energetic transition metal (Co/Cu/Zn) imidazole perchlorate complexes: Synthesis, structural characterization, thermal behavior and non-isothermal kinetic analyses

On the reaction of imidazole (IMI) with transition metal perchlorates, three novel energetic coordination compounds, [Co(IMI)6](ClO4)2, [Cu(IMI)4](ClO4)2 and [Zn(IMI)4](ClO4)2, were obtained. They were characterized by elemental analysis, FT-IR spectroscopy and X-ray single crystal diffraction. Various fascinating coordination architectures of the central metals were found in these complexes. Co is coordinated by six IMI molecules and forms an octahedral structure. The Cu and Zn atoms are coordinated by four IMI molecules and construct rectangular and tetrahedral configurations, respectively. The thermal decomposition processes of these compounds were investigated through differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and FT-IR analyses. The kinetic parameters of the exothermic peaks of the compounds were calculated by applying five integral methods and one differential method, and the most probable kinetic mechanism functions for the compounds are the same and can be described as G(α)=1−(1−α)4, f(α)=1/4(1−α)−3.

Applications of Transition Metal Perchlorates in Organic Functional Group Transformations

In view of the unique properties, like high solubility in most of the organic solvents, poor complexing ability, low charge density, stability under mild conditions and high electronegativity, transition metal perchlorates have been found to be highly effective catalysts/ reagents in wide variety of functional group transformations leading to the synthesis of large number of important organic compounds. This review presents the recent applications of important transition metal perchlorates as safe catalysts/reagents for organic functional group transformations. Keywords: Organic Synthesis, Reagents, Catalysts, Transition Metal Perchlorates.

Synthesis, crystal structures, thermal properties, and DNA-binding studies of transition metal complexes with imidazole ligands

A new series of complexes of transition metal (Cu, Zn, Ni) perchlorate with imidazole have been synthesized and characterized by elemental analysis, infrared (IR), UV-Vis spectroscopy, and single-crystal X-ray diffraction. Based on elemental and spectral data, the complexes are M(C3H4N2) x (ClO4)2 (M = Cu, Zn, x = 4; M = Ni, x = 6; C3H4N2 = imidazole). The crystal structures of Cu(C3H4N2)4(ClO4)2 (1) and Zn(C3H4N2)4(ClO4)2 (2) show metals surrounded by four nitrogens of imidazole, while the nickel complex Ni(C3H4N2)6(ClO4)2 (3) has six nitrogens of imidazole. Intra- and inter-molecular hydrogen bonds exist between hydrogen of imidazole and oxygen of perchlorate. The thermal stabilities of 1, 2, and 3 at different heating rates (β = 5°C min−1, 10°C min−1, and 15°C min−1) show that all the complexes exhibit two thermal decomposition stages; the sequence of thermal stability is 2 > 1 > 3. 1, 2, 3, and imidazole display DNA binding ability, ascertained by UV-Vis titration.

Kinetics of thermolysis of some transition metal perchlorate complexes with 1,6-diaminohexane ligand

Abstract Three transition metal perchlorate complexes of general formula [M(dah)2)](ClO4)2 (where M = Zn, Cu, and Ni; dah = 1,6-diaminohexane) have been prepared, and characterized by elemental analysis, infrared spectroscopy (IR), and gravimetric method. The thermal decomposition has been studied by thermogravimetry (TG), differential thermal analysis (DTA), and differential scanning calorimetry (DSC). Kinetics parameters of their thermolysis were evaluated by model-fitting and isoconversional methods using isothermal TG data. Model-fitting method has given the single value of activation energy (E) whereas; isoconversional method yields a series of E values which vary with the extent of conversion. Further ignition delay of these complexes was measured to see the response toward rapid heating with varying amounts. The thermal stability of the complexes decreases in the order as: [Zn(dah)2)](ClO4)2 > [Cu(dah)2)](ClO4)2 > [Ni(dah)2)](ClO4)2

Thermodynamic Properties of Inorganic Salts in Nonaqueous Solvents. VI. Apparent Molar Volumes, Expansibilities, and Compressibilities of Divalent Transition Metal Ions in Methanol and Dimethylsulfoxide

The temperature dependence of the density of divalent transition metal perchlorates in dimethylsulfoxide as well as cobalt(II), nickel(II) perchlorates, and copper(II) trifluoromethanesulfonate in methanol was determined. Moreover, sound velocities for solutions of cobalt(II), nickel(II) perchlorates, and copper(II) trifluoromethanesulfonate in methanol have been measured at 298.15 K. From these data, the partial molar volumes, partial molar expansibilities, and partial molar isentropic compressibilities have been estimated. The results obtained are discussed in terms of ion−solvent interactions.

Complex formation and photochemical properties of the crown-containing mono- and bis(styryl)bipyridine derivatives with transition metal cations

Complex formation of 15-crown-5 ether containing monoand bis(styryl)bipyridine with transition metal perchlorates was studied. The complex stoichiometry, complex structure and stability constants were determined by electronic spectroscopy. The influence of metal ions on occurrence of E,Z-isomerization was analyzed; the optical characteristics of two isomers were calculated from the photolysis data.

Preparation, X-ray crystallography and thermal decomposition of transition metal perchlorate complexes with perchlorate and 2,2′-bipyridyl ligands

Three transition metal perchlorate complexes of 2,2′-bipyridyl such as [Mn(bipy) 2(H 2O)(ClO 4)]ClO 4, [Cu(bipy)(ClO 4) 2(H 2O) 2], [Zn(bipy) 2(H 2O)](ClO 4) 2 have been prepared, and characterized by X-ray crystallography. Their thermal decomposition has been studied using iso and non-isothermal thermogravimetry (TG); differential scanning calorimetry (DSC). Kinetics parameters were evaluated by model-fitting and isoconversional methods. Their thermolytic pathways have also been suggested which involves decomposition followed by explosion. The Mn and Cu complexes decompose in single step whereas Zn complex decomposes in two steps. The coordination number of Mn and Cu atoms is found to be six and that of Zn is five. In order to evaluate the response of rapid heating, explosion delay ( D E ) measurements were undertaken. The explosion delay and activation energy were found to decrease in the order: Zn > Cu > Mn.

Adiabatic Compressibilities of Divalent Transition-Metal Perchlorates and Chlorides in N,N-Dimethylacetamide and Dimethylsulfoxide

Sound velocities of solutions of manganese(II), cobalt(II), nickel(II), copper(II), and zinc(II) perchlorates and chlorides in N,N-dimethylacetamide (DMA) and dimethylsulfoxide (DMSO) were measured at 298.15 K. Adiabatic compressibility coefficients of the solutions were determined, and apparent adiabatic molar compressibilities of the salts at infinite dilution were evaluated and discussed.

Preparation, X-ray Crystallography, and Thermal Decomposition of Some Transition Metal Perchlorate Complexes of Hexamethylenetetramine

The perchlorate complexes of manganese, nickel, and zinc with hexamethylenetetramine (HMTA) of the general formula [M(H2O-HMTA-H2O)2(H2O-ClO4)2(H2O)2] (where M=Mn, Ni, and Zn) have been prepared and characterized by X-ray crystallography. Thermal studies were undertaken using thermogravimetry (TG), differential thermal analysis (DTA), and explosion delay (DE) measurements. The kinetics of thermal decomposition of these complexes was investigated using isothermal TG data by applying isoconversional method. The decomposition pathways of the complexes have also been proposed. These were found to explode when subjected to higher temperatures.

Copper perchlorate: Efficient acetylation catalyst under solvent free conditions

Acetylation of alcohols, phenols, amines, thiols and aldehydes is performed using acetic anhydride as acylating agent and M(ClO 4) 2·6H 2O as catalyst where M is Mn, Co, Ni, Cu and Zn at room temperature under solvent free conditions. Transition metal perchlorates used here are found to be more efficient than the already reported metal triflates and s, p-block perchlorates. Substrates containing acid sensitive protecting groups are acylated successfully without any cleavage of the protection. Remarkably, less nucleophlic thiols (e.g. 2-mercaptobenzothiazole) are acylated with reasonable yields using transition metal perchlorates as catalyst whereas otherwise active acylation catalyst Mg(ClO 4) 2 was found to be inefficient.

Kinetics of thermolysis of some transition metal perchlorate complexes with 1,4-diaminobutane ligand

Three metal perchlorate complexes of general formula [M(dab) 2](ClO 4) 2·xH 2O (where M = Zn, Cu and Ni; dab = 1,4-diaminobutane) have been prepared and characterized by gravimetry, infrared spectroscopy (IR) and elemental analysis. Thermolysis has been studied by thermogravimetry (TG) in air and simultaneous thermogravimetry–differential thermogravimetry–differential thermal analysis (TG–DTG–DTA) and differential scanning calorimetry (DSC) in N 2 atmosphere. Isothermal gravimetry over the temperature range of initial decomposition of the complexes has been done to evaluate the kinetics. Both model fitting and isoconversional methods have been used for the evaluation of the kinetics. Model fitting gives a single value of activation energy ( E) whereas the isoconversional method yields a series of E values which vary with extent of conversion. Ignition with varying amounts of the complexes was measured to see the response to rapid heating. The thermal stability order of the complexes is [Zn(dab) 2](ClO 4) 2 ≫ [Cu(dab) 2](ClO 4) 2.2H 2O ≈ [Ni(dab) 2](ClO 4) 2.

Supramolecular Hydrogen-Bonded Frameworks from 6-Phosphonopyridine-2-carboxylic Acid and Transition Metal Ions

Hydrothermal reactions of 6-phosphonopyridine-2-carboxylic acid (H3L) with divalent transition metal perchlorates (Cu, Co, Ni) afforded three new organic−inorganic hybrids, namely, [Cu(C6H4NO5P)2]·...

Thermodynamic Properties of Inorganic Salts in Nonaqueous Solvents. II. Apparent Molar Volumes and Compressibilities of Divalent Transition-Metal Perchlorates in Acetonitrile

The densities of divalent transition-metal perchlorates in acetonitrile have been measured at (288.15, 293.15, 298.15, 303.15, 308.15, 313.15, and 323.15) K. From these densities, apparent molar volumes, VΦ, and partial molar volumes of the salts at infinite dilution, , as well as the expansibilities, , have been evaluated. Moreover, the apparent molar isenotropic compressibility, KS,Φ, of transition-metal perchlorates in acetonitrile have been determined from a sound velocity measurement at T = 298.15 K.

Energetic co-ordination compounds: synthesis, characterization and thermolysis studies on bis-(5-nitro-2 H-tetrazolato- N2)tetraammine cobalt(III) perchlorate (BNCP) and its new transition metal (Ni/Cu/Zn) perchlorate analogues

Bis-(5-nitro-2 H-tetrazolato- N 2)tetraammine[cobalt(III)/nickel(III)] perchlorates (BNCP/BNNP) and mono-(5-nitro- H-tetrazolato- N)triammine [copper(II)/zinc(II)] perchlorates (MNCuP/MNZnP) have been synthesized during this work. The synthesis was carried out by addition of carbonato tetraammine metal [Co/Ni/Cu/Zn] nitrate [CTCN/CTNN/CTCuN/CTZnN] to the aqueous solution of sodium salt of 5-nitrotetrazole followed by reaction with perchloric acid. The precursors were synthesized by the reaction of aqueous solution of their respective nitrates with ammonium carbonate at 70 °C. The complexes and their precursors were characterized by determining metal and perchlorate content as well as infrared (IR), electron spectra for chemical analysis (ESCA) and X-ray diffraction (XRD) techniques. The TG profiles indicated that BNCP, BNNP and MNCuP are thermally stable up to the temperature of 260–278 °C unlike MNZnP (150 °C). Sudden exothermic decomposition was observed in case of bis-(5-nitro-2 H-tetrazolato- N 2)tetraammine cobalt(III) perchlorate, bis-(5-nitro-2 H-tetrazolato- N 2)tetraammine nickel(III) perchlorate and mono-(5-nitro- H-tetrazolato- N)triammine zinc(II) perchlorate resulting in the severe damage of the sample cup. Sensitivity data indicated that the Co/Ni/Cu complexes are more friction sensitive (3–4.8 kg) than mono-(5-nitro- H-tetrazolato- N)triammine zinc(II) perchlorate (14 kg). The impact sensitivity results of the complexes corresponded to h 50% of 30–36 cm.

Thermodynamic Properties of Inorganic Salts in Nonaqueous Solvents. I. Apparent Molar Volumes and Compressibilities of Divalent Transition-Metal Perchlorates in N,N-Dimethylformamide

The densities of divalent transition-metal perchlorates in N,N-dimethylformamide have been measured over the whole composition range at (283.15, 293.15, 298.15, 303.15, 313.15, 323.15, and 333.15) K. From these densities, apparent molar volumes and partial molar volumes of the salts at infinite dilution as well as the expansibilities have been evaluated. The apparent molar isentropic compressibilities of transition-metal perchlorates in DMF have been determined from sound velocity data obtained at 298.15 K.

Apparent molar volumes of divalent transition metal perchlorates and chlorides in N, N-dimethylacetamide

Densities of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) perchlorates and chlorides in N, N-dimethylacetamide (DMA) solutions have been measured over the whole composition range at 10, 20, 25, 30, 40, 50 and 60 °C. Apparent molar volumes, partial molar volumes of the salts at infinite dilution and expansibilities have been evaluated and discussed. It has been demonstrated that the relative stability of the octahedral and tetrahedral complexes is the essential factor determining the solvation of the divalent transition metal cations solvated with N, N-dimethylacetamide molecules. Differences between volumetric properties of DMA solutions of respective perchlorates and chlorides are presented and explained in terms of formation of the chloro-complexes of the divalent transition metal cations.

Solvation and partial molar volumes of some transition metal cations in N, N-dimethylacetamide, triethylphosphate and acetonitrile

Densities of divalent transition metal perchlorates in N, N-dimethylacetamide, acetonitrile, and triethylphosphate have been measured over the whole composition range at 20, 25 and 30 °C. From these densities apparent molar volumes and partial molar volumes of the salts at infinite dilution have been evaluated and used to determine the respective ionic volumes of the solvated cations. Factors controlling the partial molar volumes of the solvated cations are discussed.

Apparent molar volumes of divalent transition metal chlorides and perchlorates in dimethyl sulfoxide solutions

Densities and apparent molar volumes for DMSO solutions of manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) perchlorates and chlorides are reported. The limiting partial molar volumes of the hexakis-(DMSO) cations are derived and discussed in terms of the ligand field effects. The differences between volumetric properties of DMSO solutions of perchlorates and chlorides are interpreted in terms of formation of the respective chloride-complexes of the divalent transition metal cations.