The liquid-crystalline properties of bis[N-[[4-[4-(alkoxy)benzoyloxy]2-hydroxyphenyl]methylene]alkanamino] complexes of Cu(II), Pd(II) and Ni(II). A general view

The thermotropic liquid-crystalline phase behaviour of a homologous set of bis[N-[[4-[4-(alkoxy)benzoyloxy]2-hydroxyphenyl]methylene]alkanamino] copper(II) complexes is examined. New data are reported and taken into account in addition to those previously reported in this Journal. The influence of alkoxy and alkanamine groups on the nature and stability of the mesophase is underlined. As a general trend, with some notable exception, smectic (C type) mesomorphism is favoured by longer alkoxy and alkanamine chains. Data concerning some Pd(II) and Ni(II) homologous complexes are also reported. The mesophase stability (nematic phase) is higher for palladium and nickel complexes than for the copper containing homologues.     

Chemometric approaches in environmental problems concerning PCDD and PCDF. Data interpretation and source correlation. Mechanisms of formation and destruction in MSW combustion process

Summary The role of multivariate analysis methods in evaluating, rationalizing, and working out complex environmental problems is discussed. The discussion is organized in two sections; a literature analysis of the application of chemometric methods to PCDD/PCDF data interpretation and source correlation and a review of the role of chemometric methods in analysing the results obtained by the Authors studying PCDD/PCDF formation and destruction mechanisms in MSW combustion processes.     

Generation of analytic semigroups by degenerate elliptic operators

We consider the generation of analytic semigroups by degenerate elliptic operators satisfying a uniform H?rmander condition under homogeneous Dirichlet boundary conditions. Received January 12, 1996     

Effects of oxygen in gamma irradiated aromatic polyesters in film

The effect of gamma irradiation in air is investigated on four thermoplastic polyesters (PET, PBT, PEN, PCT-co-ET) in films containing aromatic rings, in order to evaluate the influence of aromatic density and the role of oxygen on radiation resistance. Physical-chemical-nuclear analyses were used to this purpose. EPR measurements were carried out to detect radical stability against oxygen permeation. Viscometric investigations reported a very similar trend for all the investigated polyesters: a chain break effect that decreases at the highest doses. FT-IR analyses focused on the formation of oxidized species. Positron annihilation spectra pointed out a decrease of the intensity of ortho-positronium formation, while its lifetime remains unchanged with radiation dose.     

The behaviour of alkylcobalt carbonyls under “oxo” conditions

Both normal and secondary alkylcobalt carbonyls are shown not to undergo isomerization under catalytic “oxo” conditions, and the relevance of this obervation for the mechanism of the “oxo” reaction is discussed.     

Thermodynamic properties of organic compounds in aqueous solution. II. Apparent molal heat capacities of piperidines,morpholines, and piperazines

Apparent molal heat capacities of some piperidine, morpholine, and piperazine derivatives in aqueous solution have been determined by adiabatic calorimetry in the temperature range 20–55°C and in the molality range 0.2–1m. Comparison of experimental values with those calculated through group contributions, found for monofunctional compounds, indicates strong interactions between the hydrophilic centers. An interpretation is given of the possible mechanism of this interaction. Also, values of ΔC _p for the addition reaction of proton to nitrogen centers of mono- and bifunctional organic compounds are examined.     

Terpyridine Zn(II), Ru(III), and Ir(III) complexes: the relevant role of the nature of the metal ion and of the ancillary ligands on the second-order nonlinear response of terpyridines carrying electron donor or electron acceptor groups

Coordination of 4'-(C6H4-p-X)-2,2':6',2'-terpyridines [X = NO2, NBu2, (E)-CH=CH-C6H4-p-NBu2, (E,E)-(CH=CH)2-C6H4-p-NMe2] to Zn(II), Ru(III), and Ir(III) metal centers induces a significant enhancement of the absolute value of the second-order nonlinear optical (NLO) response of the terpyridine, measured by means of both electric field induced second harmonic generation and solvatochromic methods. By varying the nature of the metal center, the enhanced second-order NLO response shifts from positive to negative. Such a shift is controlled by electronic charge-transfer transitions, such as metal-to-ligand or ligand-to-metal transitions, in addition to the intraligand charge transfer. The enhancement generated by coordination is also controlled by the chelation effect and by fine-tuning of the ancillary ligands.     

Hydroformylation and hydrocarbethoxylation of 1,2-dicarbethoxy-1,2,3,6-tetrahydropyridazine and 1,2-dicarbethoxy-1,2,3,4-tetrahydropyridazine

The unsaturated compounds 1,2-dicarbethoxy-1,2,3,6-tetrahydropyridazine 1 and 1,2-dicarbethoxy-1,2,3,4-tetrahydropyridazine 2 have been hydroformylated and hydrocarbethoxylated in the presence of some well known cobalt, rhodium, palladium and platinum catalysts. The hydroformylation reaction can be tuned by a suitable choice of the catalyst precursor and reaction conditions, thus allowing the synthesis with high selectivity of one of the two possible isomeric aldehydes. The carbonylation reaction is less synthetically useful, since it shows low activity and unsatisfactory chemo- and regio-selectivity. However, the ester 1,2,4-tricarbethoxyhexahydropyridazine 10 can be prepared in good yield from olefin 1 by using the complex [PdCl₂(PPh₃)₂] as the catalyst precursor.