Correction: Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes.

[This corrects the article DOI: 10.1039/D2RA05341A.].

Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes.

A series of six new Cu(i) complexes with ([Cu(N-{4-R}pyridine-2-yl-methanimine)(PPh3)Br]) formulation, where R corresponds to a donor or acceptor p-substituent, have been synthesized and were used to study self-association effects on their structural and electrochemical properties. X-ray diffraction results showed that in all complexes the packing is organized from a dimer generated by supramolecular π stacking and hydrogen bonding. 1H-NMR experiments at several concentrations showed that all complexes undergo a fast-self-association monomer-dimer equilibrium in solution, while changes in resonance frequency towards the high or low field in specific protons of the imine ligand allow establishing that dimers have similar structures to those found in the crystal. The thermodynamic parameters for this self-association process were calculated from dimerization constants determined by VT-1H-NMR experiments for several concentrations at different temperatures. The values for K D (4.0 to 70.0 M-1 range), ΔH (-1.4 to -2.6 kcal mol-1 range), ΔS (-0.2 to 2.1 cal mol-1 K-1 range), and ΔG 298 (-0.8 to -2.0 kcal mol-1 range) are of the same order and indicate that the self-dimerization process is enthalpically driven for all complexes. The electrochemical profile of the complexes shows two redox Cu(ii)/Cu(i) processes whose relative intensities are sensitive to concentration changes, indicating that both species are in chemical equilibrium, with the monomer and the dimer having different electrochemical characteristics. We associate this behaviour with the structural lability of the Cu(i) centre that allows the monomeric molecules to reorder conformationally to achieve a more adequate assembly in the non-covalent dimer. As expected, structural properties in the solid and in solution, as well as their electrochemical properties, are not correlated with the electronic parameters usually used to evaluate R substituent effects. This confirms that the properties of the Cu(i) complexes are usually more influenced by steric effects than by the inductive effects of substituents of the ligands. In fact, the results obtained showed the importance of non-covalent intermolecular interactions in the structuring of the coordination geometry around the Cu centre and in the coordinative stability to avoid dissociative equilibria.

Steric and Electronic Factors Affecting the Conformation of Bimetallic CuI Complexes: Effect of the Aliphatic Spacer of Tetracoordinating Schiff-Base Ligands.

A family of six homoleptic [CuI (Ln )]2 (ClO4 )2 and six heteroleptic [CuI (Ln )(PPh3 )2 ]2 (ClO4 )2 bimetallic complexes, in which Ln are bis-Schiff base ligands with alkyl spacers of variable length (n=2-7 -CH2 -), were prepared to evaluate the role of the spacer on the formation of helicates or mesocates. In the homoleptic series, spectroscopic and theoretical studies indicate that preferences for a conformation are based on energetic parameters, mainly, the establishment of noncovalent interactions. The odd-even nature of the spacers preconditions the superposition of the aromatic rings to allow the juxtaposition necessary for noncovalent interactions, whereas the increase of the length reduces the strength of such interactions. Consequently, complexes with even-spacers of short length were identified as helicates in solution, [CuI (Ln )]22+ (n=2, 4). Complexes [CuI (Ln )]22+ (n=3-7) dissociate in solution to produce the monometallic complexes in equilibrium, [CuI (Ln )]+ . The stability of the bimetallic species is discussed in terms of their conformations. The set of heteroleptic complexes was prepared to evaluate the reach of the "odd-even rule" in the solid, which is based on the "zig-zag" arrangements of the spacers. Based on crystallographic information, "S-" and "C"-type conformations of Ln are related to even and odd spacers, respectively. This trend is considered in addition to other factors to explain preferences for either a mesocate or helicate conformation in the homoleptic series.

Crystal lattice effect on the quenching of the intracluster magnetic interaction in [V12B18O60H6](10-) polyoxometalate.

In the present work, the synthesis and structural characterization of four new polyoxovanadoborate (BVO) frameworks based on the [V12B18O60H6](10-) polyanion are reported: (NH4)8(1,3-diapH2)[V12B18O60H6]·5H2O (1), K8(NH4)2[V12B18O60H6]·18H2O (2), K10[V12B18O60H6]·10H2O (3) and K8Cs2[V12B18O60H6]·10H2O (4). A global antiferromagnetic behaviour is observed for these 10V(IV)/2V(V) mixed valence clusters. The magnetic data of 1, 2 and 3, which present different countercation environments, show that 1 is more coupled than 2 and 3. DFT calculations show that the positive charges strongly influence the polarization mechanism of the spin density of the vanadyl groups and the extent of the magnetic orbitals, therefore corroborating the experimental observation of the quenching effect of the magnetic coupling between vanadium centres of 2 and 3.

Resolution and characterization of helicate dimer and trimer complexes of 1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane with copper(I).

Complexation of copper(I) with the binucleating ligand, 1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane, mphenpr, result in formation of helical dimers, [Cu2(mphenpr)2](2+). The resolution of the enantiomeric forms of the dimers has been carried out with Δ-[As(cat)3](-) as resolving agent and X-ray structures for two compounds, P-[Cu2(mphenpr)2](Δ-[As(cat)3])2 and P-[Cu2(mphenpr)2](Δ-[As(cat)3])2·4(CH3CN), are reported. The rate of racemization in poorly-coordinating solvents has been examined by (1)H NMR, and is slow. At saturating concentrations of [[Cu2(mphenpr)2](2+)] in acetonitrile, crystals of the helical trimeric complex [Cu3(mphenpr)3](ClO4)3 are obtained. The X-ray structure of the trimer is reported. This species has also been resolved. As with the helical dimer, racemization in poorly-coordinating solvents is slow, and circular dichroism and (1)H NMR spectra are reported. The absolute configuration of the resolved complex, P-[Cu3(mphenpr)3](Δ-[As(cat)3])3, has been determined by X-ray crystallography.

Theoretical modeling of the oxidation of hydrazine by iron(II) phthalocyanine in the gas phase. Influence of the metal character.

The hydrazine oxidation by iron(II) phthalocyanine (Fe(II)Pc) has been studied using an energy profile framework through quantum chemistry theoretical models calculated in the gas phase at the density functional theory B3LYP/LACVP(d) level. We applied two models of charge-transfer mechanisms previously reported (J. Phys. Chem. A 2005, 109, 1196) for the hydrazine oxidation mediated by Co(II)Pc. Model 1 consists of an alternated loss of one electron and one proton, involving anionic and neutral species. Model 2 considers an alternated loss of two electrons and two protons and includes anionic, neutral, and cationic species. Both applied models describe how the charge-transfer process occurs. In contrast with the obtained results for Co(II)Pc, we found that the hydrazine oxidation mediated by Fe(II)Pc is a fully through-bond charge-transfer mechanism. On the other hand, the use of different charge-transfer descriptors (spin density, electronic population, condensed Fukui function) showed a major contribution of the iron atom in comparison with the cobalt atom in the above-mentioned process. These results could explain the higher catalytic activity observed experimentally for Fe(II)Pc in comparison with Co(II)Pc. The applied theoretical models are a good starting point to rationalize the charge-transfer process of hydrazine oxidation mediated by Fe(II)Pc.

Ni(II) complexes with Schiff bases derived from amino sugars.

It was found by 1H and 13C NMR spectroscopy that the Schiff base, 2-deoxy-2-(2-hydroxybenzaldimino)-D-glucopyranose exhibits enol-imine-keto-amine and anomeric equilibria in methanolic, and in dimethyl sulfoxide solutions. The reaction of the Schiff base with nickel acetate gave the bidentate, mononuclear Ni(II) complex that was characterized by spectroscopic methods and by cyclic voltammetry. The coordination of the Schiff base to the metal is through the enol-imine tautomeric form, and the anomeric equilibrium remains in dimethyl sulfoxide solutions. This complex was also obtained by reaction of D-glucosamine with Ni(II) salicylaldehydate. The same reaction was employed for the synthesis of bis-N-[2-deoxy-D-galactopyranosyl-2-(2-hydroxybenzaldiminate)]Ni(II). The small paramagnetic shifts of the 1H NMR resonances of the complexes suggest that paramagnetic species are present in low proportions.

(Acetonitrile-N)(o-benzoquinone diimine-N,N')chloro-trans-bis(triphenylphosphine-P)ruthenium(II) hexafluorophosphate 0.25-hydrate.

The Ru atom in the title compound, [RuCl(CH(3)CN){P(C(6)H(5))(3)}(2){C(6)H(4)(NH)(2)}]PF(6).0.25H(2)O, has a six-coordinate octahedral geometry, with a trans arrangement of the triphenylphosphine groups. The asymmetric unit contains two complex molecules and a partially occupied water site. Principal dimensions include Ru-N 1.958 (4)-2.044 (5), Ru-P 2.3897 (16)-2.4092 (15), and Ru-Cl 2.4280 (15) and 2.4295 (16) A

(o-Benzoquinone diimine-N,N')dichlorobis(triphenylphosphine-P)ruthenium(II) 1.33-methanol 0.33-dichloromethane solvate.

The Ru atom in the title compound, [RuCl(2){P(C(6)H(5))(3)}(2){C(6)H(4)(NH)(2)}].1.33CH(3)OH.0.33CH(2)Cl(2), shows a six-coordinate octahedral geometry, with a trans arrangement of the triphenylphosphine groups. One and a half molecules of complex, two molecules of methanol and a half molecule of dichloromethane form the asymmetric unit, with crystallographic twofold rotation symmetry for the complex molecule in a special position.

Dióxido de carbono y medio ambiente

Contenido: Ciclo natural de transformación del dióxido de carbono.- Ciclo de transformación del dióxido de carbono debido a actividades producticas

Dióxido de carbono y medio ambiente

Contenido: Ciclo natural de transformación del dióxido de carbono.- Ciclo de transformación del dióxido de carbono debido a actividades producticas