Synthesis of N,N-dialkylaminobenzonitriles and halo-(N,N-dialkyl)benzamidines by reaction of halobenzonitriles with lithium amides

3- and 4-N,N-Dialkylaminobenzonitriles and 4-chloro-(N,N-dialkyl)benzamidines were isolated by reacting 4-chlorobenzonitrile with hindered lithium amides under thermodynamic (0 °C) and kinetic control conditions (−78 °C), respectively. As previously reported, a benzyne mechanism seems to be confirmed since N,N-dialkylaminobenzonitriles are formed. Only benzamidines were isolated in fair to high yields at both 0 °C and −78 °C with non-hindered lithium amides. Exploitation and mechanistic rationale of the reaction of different halobenzonitriles are also reported.     

Synthesis,spectroscopy, electrochemistry,and methylation reaction of the dithiolate-based cobalt(II) complex derived from tert-butyl N-(2-mercaptoethyl)carbamate

A dithiolate-containing a carbamate mononuclear cobalt(II) complex namely, [Co(Boc-S)₂] (1), was obtained by the reaction of a methanolic solution of cobalt(II) nitrate hexahydrate with two equimolar amounts of the deprotonated form of tert-butyl N-(2-mercaptoethyl)carbamate (Boc-SH). The cobalt(II) complex (1) was characterized in the solid state and in solution by using FT–IR, Raman, UV–visible, and EI–mass spectroscopies, as well as thermal and X-ray diffraction studies. Spectral data showed that the carbamate (Boc-SH) acts as a mono-anionic bidentate ligand coordinating the cobalt(II) ion through two imine nitrogen and two deprotonated thiolate sulfur donor atoms in a distorted tetrahedral geometry. The thermoanalytical data evidence that the complex is stable up to 165 °C and undergoes complete decomposition, resulting in CoO. TEM imaging of the oxide residue shows its nano size clusters, suggesting that the complex (1) may be used as a precursor for nano-oxides. X-ray powder diffraction patterns evidence an isomorphism among the complex. The redox behavior of the cobalt(II) complex was also investigated by cyclic voltammetry. The reaction of the dithiolate cobalt(II) complex (1) with methyl iodide appears to occur intramolecularly with the cobalt-bound dithiolate, forming the cobalt(II)-bound dithioether complex [Co(Boc–SCH₃)₂]I₂ (2), as a dication complex with a clean second-order reaction of 13.24 × 10⁻² M⁻¹·s⁻¹.     

Selective hydrogenation by a novel palladium(II) complex

A novel insoluble green complex of palladium(II) and salicylidene ethylene diamine (salen) has been prepared and found to be an active and selective heterogeneous hydrogenation catalyst especially for the reduction of alkynes in the presence of alkenes and of alkenes in the presence of other functional groups.     

Synthesis,spectral and magnetic properties of two different 2-nitrobenzoatocopper(II) complexes containing N,N-diethylnicotinamide

Two structurally different complexes, [Cu₂(2-NO₂Bz)₄(denia)₁]_n (1) and [Cu(2-NO₂Bz)₂(denia)₂(H₂O)₂] (2), were prepared from the same reaction (where 2-NO₂Bz = 2-nitrobenzoate, denia = N,N-diethylnicotinamide) and they are reported together with [Cu₂(2-NO₂Bz)₄(DMF)₂] (3) (DMF = N,N-dimethylformamide). The compounds under study were characterized by elemental analysis, electronic, IR and EPR spectra, magnetic measurements over the temperature range of 1.8–300 K and X-ray analysis. The molecular structure of (1) is polymeric, (2) is monomeric and (3) is dimeric. In the polymeric chain of (1), the denia molecules serve as bridges between dimeric Cu₂(2-NO₂bz)₄ units. Each Cu(II) atom has a square-pyramidal arrangement with different chromophores, Cu¹O₄O′ and Cu²O₄N. The Cu–Cu distances are 2.699(1) Å in the dimeric unit and 7.980(3) Å between the dimeric units. In (2) the Cu(II) atom has a tetragonal-bipyramidal environment CuO₂N₂O′₂. In (3) two Cu(II) atoms are bridged by four carboxylate groups of four 2-NO₂bz anions in a syn–syn arrangement which create a square base about each Cu(II) atom and an apical position is occupied by the O atom of a DMF molecule (CuO₄O′). The Cu–Cu distance of 2.633(1) Å is somewhat shorter than in (1). Spectral and magnetic data of the complexes are discussed with their structures.     

(N,N-dimethylbenzylamine-2C,N)palladium(II) and -platinium(II) β-diketonates and thio-β-diketonates

(N,N-dimethylbenzylamine-2C,N)palladium(II) and -platinum(II) β-diketonates, DmbaML, have been synthesized by reaction of [DmbaMCl]₂ with the free ligand and KOH, or with the thallium(I) salt of the ligand. The various isomers formed have been investigated by ¹H and ¹⁹F NMR spectroscopy. Infrared and mass spectroscopic studies have also been made on the compounds.     

Direct photometric determination of cobalt(II) with N-methylaminothioformyl-N'-phenylhydroxylamine

N-Methylaminothioformyl-N'-phenylhydroxylamine forms a 1:2 (metal:ligand) greenish yellow complex with cobalt(II). This complex has maximum absorption at 470 nm with a molar absorptivity of 1.65 x 10(4) 1.mole(-1).cm(-1). Beer's law is obeyed over the concentration range 6 x 10(-6)-6 x 10(-5)M. The effect of diverse ions is described.     

Extraction and spectrophotometric determination of cobalt(II) with thiobenzoylacetone and simultaneous determination of cobalt and nickel

Thiobenzoylacetone in benzene is used for the extraction and spectrophotometric determination of cobalt at pH 8.4-9.1. The orange-yellow complex is measured at 460 nm. The system conforms to Beer's law over the range 0.20-4.58 microg ml of extract. The colour of the complex is stable for at least 144 hr. Cobalt(II) is quantitatively extracted and determined in the presence of 200:1 (w w ratios) of various ions. The method is made selective by using common sequestering agents such as thiourea or fluoride or by selective extraction with mesityl oxide, tributylphosphate and acetylacetone. It is possible to determine cobalt in the presence of nickel by simultaneous spectrophotometry. The method is rapid, simple, selective and sensitive.     

Simultaneous determination of cobalt(III)-copper(II) and cobalt(III)-nickel(II) mixtures by differential kinetic methods

A procedure is reported for the simultaneous determination of binary mixtures of cobalt(III)-copper(II) and cobalt(III)-nickel(II) by differential kinetic methods based on complex formation reactions with 3-(1H-1,2,4-triazolyl-3-azo)-2,6-diaminotoluene. The single-point method is used in both cases. The simultaneous determination of Co-Cu and Co-Ni is possible in the concentration range from 10/1 to 1/1. The interference caused by various ions is also studied. The method has been used to determine cobalt-copper and cobalt-nickel mixtures in synthetic samples, hydrofining catalysts and low alloy steels.     

Tetrahedral and octahedral coordination for cobalt(II) complexes of N-isopropyl-2-pyrrolidinone

Complexes of the formulas [Co(NIPP)₄](ClO₄)₂ and [Co(NIPP)₆](ClO₄)₂ have been synthesized and isolated (NIPP = N-isopropyl-2-pyrrolidinone). IR spectra and conductance data are presented as proof that perchlorate coordination in [Co(NIPP)₄](ClO₄)₂ does not occur. Vibrational spectra indicate that coordination occurs through the NIPP carbonyl oxygen for both complexes. Spectral parameters obtained from the electronic spectra and magnetic moments indicate tetrahedral and octahedral coordination for [Co(NIPP)₄](ClO₄)₂ and [Co(NIPP)₆](ClO₄)₂, respectively. The powder X-ray diffraction data appear to support the assignments of these two geometries. The crystal-field prediction that Δ(T_d)/Δ(O_h) = 0.44 is in reasonably good agreement with the experimental results.     

Three-dimensional open-framework cobalt(II) phosphates by novel routes

Two new three-dimensional open-framework cobalt phosphates, [C2N2H10]2[Co4(PO4)4]H2O, I, and [C4N3H16]3-[Co6(PO4)5(HPO4)3]H2O, II, have been prepared by the reaction of amine phosphates with Co2+ salts. I could also be prepared by the reaction of the cobalt tris amine complex with H3PO4. The crystal data for I and II are as follows: phosphate I, orthorhombic, space group P2(1)2(1)2(1) (no. 19), a = 10.277 (1) A, b = 10.302 (1) A, c = 18.836 (1) A, V = 1994.2 (2) A3, Z = 4; phosphate II, monoclinic, space group P2(1)/c (No. 14), a = 31.950 (1) A, b = 8.360 (1) A, c = 15.920 (1) A, beta = 96.6 (1) degrees V = 4223.4 (2) A3, Z = 4. The structures of both I and II are constructed from alternating CoO4 and PO4 tetrahedra. The connectivity leads to the formation of eight-membered channels in all the crystallographic directions resembling the aluminosilicate zeolite, merlinoite in the case of I and to a rather large, one-dimensional 16-membered channel in II. Strong hydrogen-bond interactions involving the amine and framework oxygen are present in both I and II.     

Three novel trinuclear zinc(II)/nickel(II) complexes with pentadentate ligands N-nitrobenzoylsalicylhydrazidate

Three trinuclear zinc(II)/nickel(II) complexes with two pentadentate ligands, N-p-nitrobenzoylsalicylhydrazidate (H₃-p-nbzshz) and N-o-nitrobenzoylsalicylhydrazidate (H₃-o-nbzshz) have been synthesized and characterized by X-ray crystallography. The complex [Zn₃(p-nbzshz)₂(C₅H₅N)₄]_n (1) molecule exhibits a one-dimensional wave-like chain structure resulting from the linkage of phenolate oxygen donor atoms of the ligands between neighboring motifs. The two nickel(II) complexes, Ni₃(p-nbzshz)₂(C₅H₅N)₄ (2) and Ni₃(o-nbzshz)₂(C₃H₇NO)₂(C₂H₆O)₂ (3) are trinuclear complexes in which three nickel(II) centers exhibit alternating square-planar and octahedral geometries. Complex 2 exhibits a curved Ni₃ metal arrangement with a Ni(1)–Ni(2)–Ni(3) angle of 62.36°, while the three nickel atoms in complex 3 are strictly linear with an angle of 180°.     

N,N,N′,N′-Tetrakis(2-hydroxyethyl)ethylenediamine palladium(II) complex as efficient catalyst for the Suzuki/Miyaura reaction in water

A new water soluble palladium(II) complex (2) derived from N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (edteH₄) (1) was synthesized in high yield and characterized by ¹H, ¹³C, HMQC and COSY NMR spectroscopy. X-ray diffraction studies on a single crystal of 2 confirmed the cis square planar geometry; the edteH₄ ligand (1) is κ² (N,N)-coordinated with four pendant CH₂CH₂OH groups. This new complex [PdCl₂(edteH₄)] (2) and the previously synthesized triethanolamine complex [Pd(OCH₂CH₂N(CH₂CH₂OH)₂)₂] (3) were tested as catalysts for the Suzuki/Miyaura cross-coupling reaction of various aryl bromides with phenylboronic acid in water. Electronically activated aryl bromides, such as 4-bromoacetophenone and 4-bromobenzaldehyde undergo the cross-coupling with extremely high turnover numbers (TON) of up to 1,00,000 without organic solvent.     

Tri- and diorganostannates containing 2-(N,N-dimethylaminomethyl)phenyl ligand

The C,N-chelated tri and diorganotin(IV) chlorides react with both protic mineral acids and carboxylic acids. The nitrogen atom of the L^CN ligand (where L^CN is 2-(dimethylaminomethyl)phenyl) is thus quarternized - protonated and new Sn-X bond (X = Cl, Br, I or the remainder of the starting acid used) is simultaneously formed. The set of zwitterionic tri and diorganostannates containing protonated 2-(dimethylaminomethyl)phenyl-moiety was prepared and structurally characterized by multinuclear NMR spectroscopy and XRD techniques. In all these cases, the intramolecular N-H?X bond is present in the molecule. Despite the central tin atom remains five-coordinated (except for the [HL^CNH]⁺[(n-Bu)₂SnCl(NO₃)₂]⁻) and reveals a distorted trigonal bipyramidal geometry, the ¹¹⁹Sn NMR chemical shift values of these zwitterionic stannates are somewhat shifted to the higher field than corresponding starting C,N-chelated tri and diorganotin(IV) halides. Reactions of C,N-chelated organotin(IV) halides with various Lewis acids are also discussed.     

Simultaneous determination of copper(II) and cobalt(II) by ion chromatography coupled with chemiluminescent detection.

In the absence of any special luminescent reagents, a weakly chemiluminescent emission was observed during the decomposition of hydrogen peroxide, catalyzed by transition-metal ions, such as Cu(II) and Co(II), in basic aqueous solution. The chemiluminescent intensity was significantly enhanced by the addition of ethyldimethylcetylammonium bromide and uranine. The signal-to-noise ratio (S/N) was proportional to the concentrations of Cu(II) and Co(II). Based on these phenomena, a flow-injection chemiluminescent method for the simultaneous separation and determination of Cu(II) and Co(II) was developed. The detection limits of the present chemiluminescent method for Cu(II) and Co(II) were 7.5 and 0.01 ng/ml, respectively. After ion chromatographic separation of Cu(II) and Co(II) by an IonPac CS5A column with oxalic acid and lithium hydroxide monohydrate as the eluent, the present chemiluminescent system was used as a post-column detector for these two transition metal ions in natural water samples.     

Theoretical study of the electron transfer reaction of hydrazine with cobalt(II) phthalocyanine and substituted cobalt(II) phthalocyanines

A theoretical model is proposed to explain the trend in reactivity of cobalt(II) phthalocyanine (CoPc) and substituted cobalt(II) phthalocyanines for the oxidation of hydrazine. Our study suggests that the reaction occurs via a through bond charge transfer pathway and not via a through space charge transfer pathway as was shown in previous work for the oxidation of 2-mercaptoethanol by CoPc (G.I. Cárdenas-Jirón and D.A. Venegas-Yazigi, J. Phys. Chem. A. 106, 11398 (2002)). We propose a mechanism for the oxidation of hydrazine based on a four-step energy profile which agrees with a mechanism proposed for the electro-oxidation of hydrazine mediated by cobalt phthalocyanines confined on a graphite electrode. We show that the step in the energy profile that involves formation of a radical of hydrazine seems to be a good starting point for the study of the transfer of the first electron in the oxidation of hydrazine mediated by different substituted cobalt(II) phthalocyanines.