A study of substituent effect on 1H and 13C nmr spectra of N‐ and C‐substituted carbazoles

¹H and ¹³C nmr spectra of several N‐ and C‐substituted carbazoles (Series 1, 2, 3 and 4) were measured. Correlations between chemical shifts and substituent constants show that these parameters describe properly the substituent effect on the nmr phenomena. Atomic charge densities for carbazoles of Series 1, 2, 3 and 4 were calculated by using the semi empirical PM3 method. These values also show a linear correlation with the ¹³C chemical shifts. The synthesis of several carbazole derivatives 1a – 1g, 2a – 2g, 3a – 3j and 4a – 4g have been carried out according to literature procedures. The carbazoles 3i, 3j and 4c have been synthesized and fully characterized for the first time.     

Vanadium Doped Sol-Gel TiO2 Coatings

A study of the experimental conditions required to obtain vanadium doped sol-gel TiO2 coatings is presented. Tetraethyl orthotitanate was employed as the TiO2 source and VCl3, VOSO4 · H2O and VOSO4 dissolved H2SO4 where employed as vanadium sources.Dip coating has been used to produce coatings on silicon wafers, spectral carbon electrodes and titanium electrodes. Both supported and unsupported films have been studied by UV-Vis spectra, IR spectroscopy and X-ray diffraction (XRD). The measurements have been made on samples as prepared and treated thermally at temperatures between 100°C and 300°C. The thermal treatment temperatures have been established from DTA/TGA measurements.The vanadium doped sol-gel TiO2 coatings have been tested as sensors for redox potential measurements in electrochemical processes. The influence of both the thickness of films and the nature of substrate has been investigated.     

How bridging ligands and neighbouring groups tune the gold-gold bond strength

Gold-gold interactions in small polynuclear complexes are analysed using extended Hückel calculations. They are influenced by the nature of the ligand donor atoms, by the bridging ligands, but most by the formal oxidation state of the metal. Au---Au bonds are much stronger in complexes of Au(II) and Au(III), but a weak interaction between two d¹⁰ centres exists for Au(I) complexes, owing to mixing of the s and p orbitals with the d orbitals. Phosphines induce stronger metal-metal bonds when coordinated trans to the Au---Au bond in [Au(II)[(CH₂)₂PPh₂]L]₂ (Ph = phenyl), but have the opposite effect when bonded orthogonally to the metal-metal axis in Au(I) binuclear species. When two gold atoms are bridged by a single carbon atom, belonging either to mesityl (Mes = 2,4,6-Me₃C₆H₂) or CR₂, the former produces stronger Au(I)---Au(I) interactions, reflected in shorter distances. Formal oxidation states are proposed for the gold atoms in two mixed-valence clusters, [Au4(C₆F₅)₂((PPh₃)_{2CH})2(PPh3)2](ClO4)2 and [{(2,4,6-C6F3H2)Au(CH2PPh2CH2)2Au{in2}-Au(CH₂PPh₂CH₂)₂Au](ClO₄)₂. The results suggest a higher oxidation state for the outer gold atoms, in both the T-shaped tetranuclear cluster and the Au₆ linear chain.     

Synthesis of fused purinoquinazolines. Three new heterocyclic ring systems

The Ullmann reaction of 8-aminotheophylline or 8-aminocaffeine with 2-chlorobenzoic acid and of 8-bromotheophylline with ethyl-2-aminobenzoate afforded derivatives of three new heterocyclic systems: purino[7,8-α]quinazoline-5,9,11(6H,8H,10H)-trione, purino[8,9-b]quinazoline-2,4,11(1H,3H,5H)-trione and purino[8,7-b]quinazoline-2,4,6(1H,3H,11H)-trione, respectively.     

The structures and formation of [C4H6N]+ ions 2—ion structures derived from 2-methylpropanenitrile

The loss of a hydrogen atom from ionized 2-methylpropanenitrile is preceded by a drastic rearrangement of the molecular ion. The result of this fragmentation is the generation of two stable structurally different [C₄H₆N]⁺ ions, formed via different pathways. Their structures can be established by a careful comparison of the metastable ion spectra, collision activation spectra, and charge stripping spectra from the compound and its three deuterium labeled analogues and from [C₄H₆N]⁺ ions generated from reference compounds via electron impact ionization or in selected ion/molecule reactions.     

Crystal structures and magnetic properties of two low-dimensional materials constructed from [Mn(III)(salen)H2O]+ and [M(CN)8](3-/4-) (M = Mo or W) precursors

The syntheses, X-ray structures, and magnetic behaviors of two new cyano-bridged assemblies, the molecular [Mn(III)(salen)H2O]3[W(V)(CN)8].H2O (1) and one-dimensional [Mn(salen)(H2O)2]2[[Mn(salen)(H2O)][Mn(salen)]2[Mo(CN)(8)]].0.5ClO4.0.5OH.4.5H2O (2), are presented. Compound 1 crystallizes in the monoclinic system, has space group P2(1)/c, and has unit cell constants a = 13.7210(2) A, b = 20.6840(4) A, c = 20.6370(2) A, and Z = 4. Compound 2 crystallizes in the triclinic system, has space group P, and has unit cell dimensions a = 18.428(4) A, b = 18.521(3) A, c = 18.567(4) A, and Z = 2. The structure of 1 consists of the asymmetric V-shaped Mn-NC-W-NC-Mn-O(phenolate)-Mn molecules, where W(V) coordinates with [Mn(salen)H2O] and singly phenolate-bridged [Mn(salen)H2O]2 moieties through the neighboring cyano bridges. The [W(V)(CN)8]3- ion displays distorted square-antiprism geometry. The structure of 2 consists of the cyano-bridged [Mn3(III)Mo(IV)]n- repeating units linked by double phenolate bridges into one-dimensional zigzag chains. The Mn(III) centers are bound to Mo(IV) of square-antiprism geometry through the neighboring cyano bridges. The magnetic studies of 1 reveal the antiferromagnetic intramolecular interactions through the CN and phenolate bridges and the relatively weak intermolecular interactions. Compound 1 becomes antiferromagnetically ordered below TN = 4.6 K. The presence of the magnetic anisotropy is documented with the MH measurements carried out for both polycrystalline and single-crystal samples. At T = 1.9 K, the spin-flop transition is observed in the field of 18 kOe applied parallel to the bc plane, which is the easy plane of magnetization. Field dependence of magnetization of 1 shows field-induced metamagnetic behavior from the antiferromagnetic ground state of ST = 3/2 to the state of ST = 5/2. The magnetic properties of 2 indicate a weak antiferromagnetic interaction between Mn(III) centers in double-phenolate-bridged [Mn(III)(salen)]2 dinuclear subunits and a very weak ferromagnetic interaction between them through the diamagnetic [Mo(IV)(CN)8]4- spacer.     

Enhancing selectivity in oxidation catalysis with sol-gel nanocomposites

Valuable organic compounds such as alpha-hydroxy acids are easily synthesised with relevant selectivity enhancement using a sol-gel hydrophobized nanostructured silica matrix doped with the organocatalyst TEMPO: A materials science based synthetic route which cannot be achieved via classical homogeneous synthesis.     

Vilsmeier formylation of 5,10,15-triphenylcorrole: expected and unusual products

5,10,15-Triphenylcorrole (1) reacts with the Vilsmeier reagent (POCl(3)/DMF) to give the corresponding 3-formyl derivative 3 as the major product. The regioselectivity of the reaction was proven by X-ray crystallography and only traces of the 2-formyl isomer were observed. A more polar product is also observed and this compound becomes the major product when an excess of DMF is used for the preparation of the Vilsmeier reagent, while the formation of the 3-formyl isomer is almost completely suppressed. X-ray crystallography allowed us to identify this compound as the fully substituted N-ethane bridged derivative 4, formed from the attack of the Vilsmeier reagent at the inner core of the macrocycle. This compound is unique among porphyrinoid macrocycles, and further confirms the peculiarity of corrole chemistry.     

The interphase between mercury and acetone+ nitromethane mixtures with KPF6 as a supporting electrolyte

Differential capacity and interfacial tension measurements were carried out on mercury for acetone+nitromethane mixtures with KPF₆ as a supporting electrolyte. On the basis of Gibbs adsorption equation and Guggenheim's model of the surface phase the composition of the surface layer was estimated for different acetone contents and different charges on the mercury electrode. The results obtained indicate that the positive acetone adsorption is marked at negative charges with maximum at σ_m=?0.07 C m^?2, but is practically non-existent at zero and positive charges.     

pH controls the rate and mechanism of nitrosylation of water-soluble FeIII porphyrin complexes

In-depth kinetic and mechanistic studies on the reversible binding of NO to water-soluble iron(III) porphyrins as a function of pH revealed unexpected reaction kinetics for monohydroxo-ligated (P)Fe(III)(OH) species formed by deprotonation of coordinated water in diaqua-ligated (P)Fe(III)(H(2)O)(2). The observed significant decrease in the rate of NO binding to (P)Fe(OH) as compared to that of (P)Fe(H(2)O)(2) does not conform with expectations based on previous mechanistic work on NO-heme interactions, which would point to a diffusion-limited reaction for the five-coordinate Fe(III) center in (P)Fe(OH). The decrease in rate and an associatively activated mode of NO binding observed at high pH is ascribed to an increase in the activation barrier related to spin state and structural changes accompanying NO coordination to the high-spin (P)Fe(III)(OH) complex. The existence of such a barrier has previously been observed in the reactions of five-coordinate iron(II) hemes with CO and is evidenced for the first time for the process involving coordination of NO to the iron heme complex. The observed reactivity pattern, relevant in the context of studies on NO interactions with synthetic and biologically important hemes (in particular, hemoproteins), is reported here for an example of a simple water-soluble iron(III) porphyrin [meso-tetrakis(sulfonatomesityl)porphinato]-iron(III), (TMPS)Fe(III).