Driving forces in substitution reactions of octahedral complexes: The influence of the competitive effect

The reaction of cis-[RuCl₂(P–P)(N–N)] type complexes (P–P = 1,4-bis(diphenylphosphino)butane or (1,1′-diphenylphosphino)ferrocene; N–N = 2,2′-bipyridine or 1,10-phenantroline) with monodentate ligands (L), such as 4-methylpyridine, 4-phenylpyridine and benzonitrile forms [RuCl(L)(P–P)(N–N)]⁺ species. Upon characterization of the isolated compounds by elemental analysis, ³¹P{¹H} NMR and X-ray crystallography it was found out that the type of the L ligand determines its position in relation to the phosphorus atom. While pyridine derivatives like 4-methylpyridine and 4-phenylpyridine coordinate trans to the phosphorus atom, the benzonitrile ligand (bzCN), a good π acceptor, coordinates trans to the nitrogen atom. A ³¹P{¹H} NMR experiment following the reaction of the precursor cis-[RuCl₂(dppb)(phen)] with the benzonitrile ligand shows that the final position of the entering ligand in the complex is better defined as a consequence of the competitive effect between the phosphorus atom and the cyano-group from the benzonitrile moiety and not by the trans effect. In this case, the benzonitrile group is stabilized trans to one of the nitrogen atoms of the N–N ligand. A differential pulse voltammetry experiment confirms this statement. In both experiments the [RuCl(bzCN)(dppb)(phen)]PF₆ species with the bzCN ligand positioned trans to a phosphorus atom of the dppb ligand was detected as an intermediate complex.     

High-performance liquid chromatography enantioseparation of proton pump inhibitors using the immobilized amylose-based Chiralpak IA chiral stationary phase in normal-phase, polar organic and reversed-phase conditions

The chiral resolving ability of the amylose-based Chiralpak IA chiral stationary phase towards omeprazole and other proton pump inhibitors under reversed-phase conditions was investigated. Organic modifier-buffer demonstrated to be a valid alternative elution mode with respect to conventional polar organic and normal-phases. No evidence of deterioration of performance of the enantioselective column after several multimodal cycles of elution was observed. Mobile phase composition was systematically changed in order to modulate the enantiomer elution order of set of compounds studied. A very simple method based on on-line detection of optical rotational sign during enantioselective HPLC was developed to assign the absolute configuration and enantiomeric elution order.     

Photon upconversion based on sensitized triplet–triplet annihilation

Photon upconversion, the process wherein light of long wavelength is frequency converted to photons of higher energy, is readily achieved at low incident power through sensitized triplet–triplet annihilation (TTA) in various chromophore combinations spanning the UV to the near-IR. This emerging wavelength-shifting technology truly represents a viable route towards converting low energy terrestrial solar photons into light adequate to drive electron transfer in operational photovoltaics. Generalized molecular design constraints, all operational examples reported to date, and measurement techniques applied to these low power nonlinear processes are reviewed in this contribution. In many instances, direct visualization of this phenomenon is presented in solution and within various polymeric host materials.     

Molecular and Supramolecular Structures of 1‐Phenyl‐4‐phenylacetyl‐2‐thiosemicarbazide (H2L) and its Complexes with Diphenyllead(IV) Chloride and Acetate

Reaction of 1‐phenyl‐4‐phenylacetyl‐2‐thiosemicarbazide (H₂L) with diphenyllead(IV) dichloride and acetate afforded the complexes [PbPh₂Cl₂(H₂L)₂] and [PbPh₂L]. The ligand and the complexes were characterized by elemental analyses, ¹H and ¹³C NMR spectroscopy and X‐ray crystallography. In the asymmetric unit of crystals of the ligand there are four independent molecules of H₂L and four molecules of water, which associate in the lattice as two independent sheets. The complex [PbPh₂Cl₂(H₂L)₂]·4MeOH has slightly distorted all‐trans octahedral geometry around the lead atom, and the fact that the ligand is S‐bound rather than O‐bound suggests that PbPh₂Cl₂ behaves as a “soft” Lewis acid. Hydrogen bonds involving NH groups, Cl atoms and MeOH molecules form a three‐dimensional supramolecular structure. In [PbPh₂L]·Me₂CO, the L^2? anion bridges between two metal centres, binding to one strongly via the N and S atoms and weakly via the O atom, and to the other via the O atom, thus creating polymeric chains along the b axis. The double deprotonation and metallation of H₂L induce significant changes in its configuration and lengthen the C‐S and C‐O bonds, suggesting an evolution of the dianion towards a thiol‐enol form.     

Scaling and universality in proportional elections

A most debated topic of the last years is whether simple statistical physics models can explain collective features of social dynamics. A necessary step in this line of endeavor is to find regularities in data referring to large-scale social phenomena, such as scaling and universality. We show that, in proportional elections, the distribution of the number of votes received by candidates is a universal scaling function, identical in different countries and years. This finding reveals the existence in the voting process of a general microscopic dynamics that does not depend on the historical, political, and/or economical context where voters operate. A simple dynamical model for the behavior of voters, similar to a branching process, reproduces the universal distribution.     

Wavelength-dispersive spectral analysis and quantification of monazites by electron-probe microanalysis

The problem of determining the chemical composition of monazite grains through electron probe microanalysis is studied, by using a scanning electron microscope with a wavelength dispersive spectrometer. A careful qualitative analysis is performed with the purpose of determining all the elements present in the samples, the lines to be used in the quantifications trying to minimize interferences, the angular positions and the acquisition times for the measurement of peak and background intensities and the crystals to be used. Particular emphasis is devoted to the analysis of Th, U and Pb, which are used to determine the age of the rock by means of the U-Th-Pb method, commonly used in geochronology. Quantitative determinations of the chemical composition of monazite grains are performed, optimizing the experimental conditions on the basis of the qualitative analysis. The determinations were made under two different criteria of quantification of oxygen, and the dissimilar results obtained are discussed.     

Diversity through a branched reaction pathway: generation of multicyclic scaffolds and identification of antimigratory agents

A library of 91 heterocyclic compounds composed of 16 distinct scaffolds has been synthesized through a sequence of phosphine-catalyzed ring-forming reactions, Tebbe reactions, Diels-Alder reactions, and, in some cases, hydrolysis. This effort in diversity-oriented synthesis produced a collection of compounds that exhibited high levels of structural variation both in terms of stereochemistry and the range of scaffolds represented. A simple but powerful sequence of reactions thus led to a high-diversity library of relatively modest size with which to explore biologically relevant regions of chemical space. From this library, several molecules were identified that inhibit the migration and invasion of breast cancer cells and may serve as leads for the development of antimetastatic agents.     

Synthesis and characterization of tris(heteroleptic) Ru(II) complexes bearing styryl subunits

We have developed and optimized a well-controlled and refined methodology for the synthesis of substituted π-conjugated 4,4'-styryl-2,2'-bipyridine ligands and also adapted the tris(heteroleptic) synthetic approach developed by Mann and co-workers to produce two new representative Ru(II)-based complexes bearing the metal oxide surface-anchoring precursor 4,4'-bis[E-(p-methylcarboxy-styryl)]-2,2'-bipyridine. The two targeted Ru(II) complexes, (4,4'-dimethyl-2,2'-bipyridine)(4,4'-di-tert-butyl-2,2'-bipyridine)(4,4'-bis[E-(p-methylcarboxy-styryl)]-2,2'-bipyridine) ruthenium(II) hexafluorophosphate, [Ru(dmbpy)(dtbbpy)(p-COOMe-styryl-bpy)](PF(6))(2) (1) and (4,4'-dimethyl-2,2'-bipyridine)(4,4'-dinonyl-2,2'-bipyridine)(4,4'-bis[E-(p-methylcarboxy-styryl)]-2,2'-bipyridine) ruthenium(II) hexafluorophosphate, [Ru(dmbpy)(dnbpy)(p-COOMe-styryl-bpy)](PF(6))(2) (2) were obtained as analytically pure compounds in high overall yields (>50% after 5 steps) and were isolated without significant purification effort. In these tris(heteroleptic) molecules, NMR-based structural characterization became nontrivial as the coordinated ligand sets each sense profoundly distinct magnetic environments greatly complicating traditional 1D spectra. However, rational two-dimensional approaches based on both homo- and heteronuclear couplings were readily applied to these structures producing quite definitive analytical characterization and the associated methodology is described in detail. Preliminary photoluminescence and photochemical characterization of 1 and 2 strongly suggests that both molecules are energetically and kinetically suitable to serve as sensitizers in energy-relevant applications.