Ni(II) complexes with (AE)-trans-N,N 0 -bis(salicylidene)-1,2-cyclohexanediamine ([Ni(salcn)]), and its methyl ([Ni(salcn(Me))]) and tert-butyl ([Ni(salcn(Bu))]) derivatives have been synthesized. Anodic electropolymerization has been used to form electrodes modified by polymer films. FTIR and FTIR ATR methods showed that the obtained films consist of polymers of phenyl-phenyl type. The structure of poly[Ni(salcn)] is built with 1,2,4-and 1,2,3,5-substituted chains. A three-step process of the oxidation of the complexes and their films has been ascertained on the basis of cyclic voltammetry measurements.Furthermore we have also detected the oxidized species which probably serve as intermediates for polymer formation. The influence of the substituent in the phenolate moiety on the type of reaction after which the dimerization and polymerization reaction occurs has been evidenced. Furthermore the substituent dependence on the stability of the phenoxyl radical complex and the Ni(II)-phenoxonium cation has been noticed. For the [Ni(salcn(Bu))] complex, an additional electropolymerization step -the adsorption of the reagent on the electrode surface -has been observed. † Electronic supplementary information (ESI) available: Table S1. Comparison of the FTIR ATR bands of poly[Ni(salcn)] films (electrosynthesized in Bu 4 NPF 6 or Bu 4 NClO 4 ) with the FTIR bands of the [Ni(salcn)] complex; Fig. S1. Cyclic voltammograms of complexes in TBAH/CH 2 Cl 2 , 0.1-1.6 V, v = 0.05 V s À1 , 1st scans vs. Ag/AgCl and Fig. S2. Cyclic voltammograms of complexes in TBAH/CH 2 Cl 2 , 0.1-2.1 V, v = 0.05 V s À1 , 1st scans vs. Ag/AgCl. See
The effect of a ligand structure on the catalytic activity of salophen chromium(iii) complexes in the ring-opening copolymerization of phthalic anhydride with a series of epoxides was studied.
Instruments.-Spectroelectrochemistry measurements were carried out by SPELEC DROPSENS with reflection probe UV-VIS.Cyclic voltammetry, chronocoulometry and chronopotentiometry measurements were performed using AUTOLAB PGSTAT 10 Eco Chemie in three-electrode system. A Pt disk electrode (from MIN-ERAL) modified with polymer nickel complexes (Ptpoly) were used as a working electrode. The surface area of the Pt disk electrode (0.1865 cm 2 ) was determined voltammetrically using potassium hexacyanoferrate(III) solution as a standard. 33 A Pt plate was used as a counter electrode and Ag/AgCl (1 mol•dm -3 NaCl) a reference electrode, was connected to the bulk of the solution by a Luggin capillary.Voltammograms were recorded in the potential range of 0 V to 2.1 V, at sweep rates between 0.01 and 2 V•s −1 .Chronocoulometry were carried out using two different potential steps, for different times of potential step (10 −3 ÷ 30 s). The first step
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