Mössbauer studies on one-dimensional iron phthalocyanines

Summary Magnetic moments and⁵⁷Fe Mössbauer spectra at room temperature and at liquid nitrogen temperature of polynuclear ligand-bridged iron phthalocyanines, FePcL (L = pyrazine and 4,4-bipyridyl), are reported. The experimental data are in agreement with a pseudo-octahedral environment around the iron(II) cation. Partially oxidized derivatives, FePc(pz)I_0.26 and FePc(bipy)I_1.06 have been synthesized and their⁵⁷Fe Mössbauer spectra and magnetic moments within the same temperature range obtained. Oxidation is shown to be metal centred and the iodine is found to be in I^– form for FePc(pz)_0.26 and as both I^– and I ₃ ^– species for FePc(bipy)I_1.06. While the magnetic moment of FePc(pz) increases upon oxidation, the opposite occurs for FePc(bipy).     

Synthesis and characterization of new di- and tri-nuclear cyano-bridged bis(dioximato)cobalt(III) complexes

Summary Several new neutral and cationic di- and tri-nuclear cyano-bridged bis(dioximato)cobalt(III) complexes have been synthesized and characterized (dioximato = dimethylglyoximato or diphenylglyoximato). These compounds are obtained through substitution of labile axial ligands by the nitrogen of the cyano-group in [Co(dioximato)₂(CN)₂]^– or [LCo(dioximato)₂(CN)] (L = H₂O, NH₃, or py). In the first case, the existence of only one band in the CN-stretching region of the i.r. spectrum at 2190–2200 cm^–1 is indicative of a trinuclear compound, while the presence of a second band at 2140 cm^–1 attributable to a terminal cyano-group indicates a dinuclear structure. In the presence of water, aquation of axial positions may take place at the same time as bridge formation, whereas the use of a non-aqueous solvent allows the preparation of complexes with pyridine or NH₃.     

Complex emulsion inversion pattern associated with the partitioning of nonionic surfactant mixtures in the presence of alcohol cosurfactant

Commercial ethoxylated nonionic surfactant mixtures containing alcohol cosurfactant exhibit a three-phase behavior whose formulation strongly varies with the water/oil ratio. As a consequence, a change in water/oil ratio can result in a sequence of up to three different emulsion inversion processes, through a combination of formulation and composition effects.     

The nature of the AuI ... AuI Interactions between Cationic [AuL2]+ Complexes in the Solid State

The interaction energy of a [Au{C(NHMe)₂}₂]⁺ ... [Au{C(NHMe)₂}₂]⁺ dimer is investigated using the MP2 method and the LANL2DZ basis set when isolated or embedded in ionic an [Au{C(NHMe)₂}₂]₂anion₂ aggregate, a good model for the environment that these dimers feel in ionic crystals. A repulsive interaction energy is obtained when the dimer is isolated. However, it is possible to find short Au^I ... Au^I separations in [Au{C(NHMe)₂}₂]₂anion₂ aggregates, because in these aggregates the sum of the cation ... anion interactions overweight the sum of the cation ... cation plus anion...anion interactions. This explains why short Au^I ... Au^I separations are found in ionic crystals. The Au^I ... Au^I interaction found in [Au{C(NHMe)₂}₂]₂ anion₂ aggregates shows the same features observed in energetically stable dimers presenting Au^I... Au^I bonds. This makes appropriate to use the name counterion-mediated bonds for the Au^I... Au^I interactions found in [Au{C(NHMe)₂}₂]₂ anion₂ aggregates and ionic crystals.     

Benzylic cleavage and McLafferty rearrangement under electron ionization conditions in the fragmentation of 5,6-dialkyl-2, 4-diarylpyrimidines

Several 5,6-dialkyl-2,4-diarylpyrimidines were prepared and their electron ionization (EI) mass spectra reported. The benzylic cleavage takes place easily together with an important McLafferty rearrangement. The involvement of the nitrogen atom appears to be important in the fragmentation of 5-methyl-substituted pyrimidines. In contrast, the 6-methyl-substituted pyrimidines undergo benzylic cleavage without hydrogen transfer. Thus, the difference in the mass spectrometric behaviour allows the identification of these isomeric compounds which, in contrast, exhibit only small differences in their NMR spectra. Copyright 1999 John Wiley & Sons, Ltd.     

Convenient synthesis of nucleoside and isonucleoside analogues

[reaction: see text]. A very simple methodology to stereoselectively achieve tricyclic isonucleosides (nucleobase = thymine, uracil, and 5-fluoruracil) and 3'-C-branched nucleosides (nucleobase = theophylline) was performed by means of a DBU-mediated addition process using a readily available 2-bromo sugar. The mechanism for these transformations implies the loss of both substituents at C-2 and C-3 on the sugar moiety, and although it seems that DBU is probably involved, its involvement has not yet been ascertained. Cytosine did not react under these conditions.     

A pyrimidine thiolate Rh(I) complex: structure, bonding and one-dimensional interactions in solid and in solution

The reaction of [Rh(micro-Cl)(COD)]2 with 4,6-dimethyl-pyrimidinethiolate (Me2-pymt) and subsequent substitution of COD by CO yields [Rh(Me2-pymt)(CO)2]. The stacking pattern found in this compound is in contradiction with previously studied comparable square-planar complexes of type d8-[M(chelate)(monodentate)2] in which each ligand has different pi-acidic character. A theoretical study of the intermolecular interactions and conformation of the title compound has been carried out, combining semi-empirical band calculations on the real chains and ab initio(MP2 level) calculations on a model dimer. The combination of electronic and steric effects determines the rotation of the successive monomers and the deviation from linearity of the one-dimensional stacks. Its behaviour in solution is also special, developing a blue colour and forming micelles, when adding water to acetone solutions.     

Selecting an agricultural technology package based on the flexible and interactive tradeoff method

Annals of Operations Research - The aim of this paper is to solve an agricultural technology packages selection problem by considering multiple dimensions which influence a maize producer’s...     

Continuous chirality measures in transition metal chemistry

The definition of the continuous chirality measure(CCM) is provided and its applications are summarized in this tutorial review, with special emphasis on the field of transition metal complexes. The CCM approach, developed in recent years, provides a quantitative parameter that evaluates the degree of chirality of a given molecule. Many quantitative structural correlations with chirality have been identified for most of the important families of metal complexes. Our recent research has shown that one can associate the chirality measures with, e.g., enantioselectivity in asymmetric catalysis. We also explore a fragment approach to chirality in which we investigate which part of a molecule is responsible for the chirality-associated properties of a given family of compounds.