R. D. Rakhimov

Copper–Bispidine Complexes: Synthesis and Complex Stability Study

A new series of dicarboxylic derivatives of bispidines have been synthesized to develop novel copper(II) complexes suitable as imaging agents for positron emission tomography. For characterization purposes, copper complexes of bispidines were synthesized in the pure form and in quantitative yields by neutralization of ligands with malachite. The formation of complexes and their stoichiometries were studied by potentiometric titration, cyclic voltammetry, and spectroscopic methods. The stability constants were found to be fairly suitable for copper cation fixation inside dianionic chelate molecules.

New supramolecular synthons based on 3d transition metal complexes with bidentate bispidines: synthesis and structural, spectroscopic, and electrochemical studies

A new supramolecular synthon, a 2L: 1M complex of bidentate bispidine with transition metal, was suggested. A number of complex compounds of 1,5-dimethylbispidin-9-one with Cuii, Niii, and Coii salts (perchlorates, chlorides, bromides, nitrates, trifluoroacetates) were synthesized. The structure and composition of complexes obtained were estimated based on the combination of physicochemical methods of analysis (elemental analysis, X-ray diffraction analysis, NMR, IR, and Raman spectroscopy, electron absorption spectroscopy, ESI mass spectrometry, CVA). The composition of most complexes in the solid state corresponds to the formula ML2X2, and in a number of cases the fragment [ML2]2+ is retained in solution, which was shown by NMR spectroscopy for nickel complexes and by mass spectrometry for copper complexes. In the case of copper chloride, the composition of the acetonitrile solutions in the presence of the ligand depends on the ratio of starting compounds and their concentration: an increase in proportion of CuCl2 and concentration shifts the equilibrium to the side of complexes with higher nuclearity. A 2L: 1M complex of bispidine with metal was for the first time structurally characterized using copper(ii) nitrate derivative as an example. The CVA method showed existence of reversible electrochemical reduction of the metal for a number of complexes (the products of the reaction of 1,5-dimethylbispidin-9-one with nickel(ii) and cobalt(ii) chlorides, as well as with nickel(ii) bromide). According to the IR and Raman spectra, chelation of metals with 1,5-dimethylbispidin-9-one leads to the shift of the absorption band of the ligand carbonyl group from 1700 to 1721–1744 cm−1. Nickel(ii) and copper(ii) perchlorates and nitrates were concluded to be the most promising complexation agents for the binding of two NH,NH-bispidine ligands in a coordination polymer.

Complexation properties of 3,7-diazabicyclo[3.3.1]nonanes

The electrochemical behavior of some 3,7-diazabicyclo[3.3.1]nonanes and their complexes with copper(II) chloride was investigated. The composition and stability of complexes are discussed.

Bis[4-(methylthio)phenylmethyleneaminophenyl] disulfide, 2-[4-(methylthio)phenyl]-2,3-dihydro-1,3-benzothiazole, and its nickel(II) and cobalt(II) complexes: Synthesis, adsorption on gold surface and electrochemical characterization

2-[4-(Methylthio)phenyl]-2,3-dihydro-1,3-benzothiazole (1) and bis[4-(methylthio)phenylmethylene-aminophenyl] disulfide (2) were synthesized. Novel coordination compounds of Ni(II) and Co(II) with 2-[4-(methylthio)phenylmethyleneamino]thiophenol, M(1)2 (M=Co (3); M=Ni (4)), were prepared by reacting 1 with M(OAc)2·6H2O or MCl2·6H2O in EtOH solution. The structure of 2 was proved by X-ray crystallography. Electrochemical behavior of 1–4 in CH3CN solution and at the surface of a gold electrode was studied by cyclic voltammetry. The modification of the electrode by ligand 1 and its complexes with Ni2+ and Co2+ is described in detail. Two procedures were used to obtain a self-assembled monolayer of a metal complex on the gold surface: the adsorption of prepared coordination compound 3 or 4 on the electrode and the initial modification of the electrode with ligand 1 followed by the formation of a coordination complex between the ligand adsorbed on the electrode and a metal salt occurring in solution. On the basis of the electrochemical data, it was found that the structure of complexes formed on the surface differs from that of the complexes produced in solution.

A new approach to ferrocene derived alkenes via copper-catalyzed olefination

Summary A new approach to ferrocenyl haloalkenes and bis-alkenes was elaborated. The key procedure involves copper catalyzed olefination of N-unsubstituted hydrazones, obtained from ferrocene-containing carbonyl compounds and hydrazine, with polyhaloalkanes. The procedure is simple, cheap and could be applied for the utilization of environmentally harmful polyhalocarbons. The cyclic voltammetry study of the representative examples of the synthesized ferrocenyl alkenes shows the strong dependence of the cathodic behavior on the amount of vinyl groups: while for the monoalkene containing molecules no reduction is seen, the divinyl products are reduced in several steps.

Electrochemical activation of the alkylation of GeI2 byn-butyl bromide and methylcobalt(iii) bisdimethylglyoximate

The mechanism of the alkylation of GeI2 byn-butyl bromide and methylcobalt(iii) bisdimethylglyoximate in acetonitrile was studied using cyclic voltammetry. The reaction with the methylcobalt complex occursvia anodic activation (oxidation of the methylcobalt complex), while the reaction withn-butyl bromide is initiated by cathodic activation (reduction of GeI2).

Electrochemical study of redox properties of 2,3,4,5-tetraphenyl-1-heterocyclopenta-2,4-dienes Ph4C4ER1R2 (E = Si, Ge, Sn). A new method for generation of tetraphenylgermole dianion

The electrochemical behavior of the sila-, germa-, and stannacyclopentadienes (metalloles) was studied by cyclic voltammetry. The oxidation and reduction mechanisms of these heterocyclic compounds were investigated. A new method for generation of tetraphenylgermole dianion involving the electrochemical reduction of the corresponding dichlorogermole is proposed. Electrochemical oxidation of the metallole dianions was first studied taking tetraphenylgermole dianion as an example.

Single-electron transfer upon formation of 2,2,3,3-tetracyano-1-phenyl-7,8-dithiabicyclo[3.2.1]octane from allyl dithiobenzoate and tetracyanoethylene. Electrochemical investigations

Studies by the method of cyclic potential scanning from 0.2 to 1.9 V provided electroanalytical evidence that the reaction of allyl dithiobenzoate with tetracyanoethylene (TCNE) in MeCN proceeds as the reaction of the TCNE.− radical anion with the PhSSAll.+ radical cation to form phenyl-substituted 2,2,3,3-tetracyano-7,8-dithiabicyclo[3.2.1]octane. When current is not applied, the reaction does not proceed at 20°C for 3 days. However, this reaction in boiling MeCN occurs without electrochemical activation and, apparently, involves intermediate formation of the above radical ions. It was established by semiempirical PM3 calculations that allyl dithiobenzoate and TCNE form a stable charge-transfer complex that precedes chemical electron transfer.

Experimental and theoretical studies of anions of transition-metal chelate complexes in alkylation reactions at a metal atom

Electrochemical reduction of a number of chelate complexes of transition metals (Chel)2M or (Chel)2MXY (M=Co, Rh, Ir, or Ni; Chel are anions of dmgH (dmg is dimethylglyoxime), (3,5-di-tert-butyl-4-hydroxyphenyl)mgH (mg is methylglyoxime),N-aryl-3-methoxysalicylaldoxime,N-aryl-3-methyl-2-thiocarboxamidopyridine, or 2-acetylindan-1,3-dione; X=Y=py, Ph3P, or H2O or X=Cl and Y=Ph3P) in MeCN or DMF was studied using the cyclic voltammetry and rotating disk electrode techniques. Under the action of BunBr, some electrochemically generated anions [(Chel)2M]− enter into the rather fast alkylation reactions (apparently, at the metal atom) to form (Chel)2M—Alk. The geometries of four model neutral and anionic cobalt complexes were calculated using the semiempirical ZINDO/1 method. According to calculations, the transformation of the neutral complex (Chel)2M into the anion [(Chel)2M]− leads to a change in the configuration from square-planar to square-pyramidal or from tetrahedral to disphenoid. The effects of steric hindrances, the HOMO energies, and the charge of the metal atom in the anionic complexes on the alkylation reactions at the metal atom are discussed.

Alkylation of cobalt and lutetium tetra(3,5-di-tert-butyl-4-hydroxyphenyl)dodecachlorophthalocyanine complexes initiated with current

Electrochemical properties of tetra(3,5-di-tert-butyl-4-hydroxyphenyl)dodecachlorophthalocyanine complexes of cobalt(II) and lutetium(III) in DMF solutions have been studied. It was suggested that in the presence ofn-butyl bromide, the electrochemically generated monoanionic complexes undergo alkylation at the metal atom. The geometries of the neutral and anionic complexes were calculated by the ZINDO/I semiempirical method.