Density functional study on electronic structures and reactivity in methyl‐substituted chelates used in organic light‐emitting diodes

The electronic structure and reactivity trends of a set of tris‐(n‐methyl‐8‐quinolinolato) metal (III) (n = 0, 3, 4, 5; metal = Al⁺³, Ga⁺³) used as electron‐transport layer in organic light‐emitting diodes were studied and compared. All geometries were optimized at B3LYP/6‐31G(d,p) level of theory. The geometries of the ground state (S₀) of unsubstituted molecules AlQ3 and GaQ3 were found to be slightly affected by the methyl group, which is in agreement with previous works. Methyl‐derivatives conserve largely the electronic structures of AlQ3 and GaQ3. The energies of the frontier orbitals highest occupied and lowest unoccupied molecular orbital are raised by the electron‐releasing effect of methyl group. Molecular orbital contribution analysis reveals that the orbital population is essentially the same for both MQ3 and their derivatives. Analyses of the ionization potential and electron affinity showed that MQ3 tend to be better hole‐blockers than methylated analogues and 5Me‐MQ3 have higher hole‐injection capability than the other methyl‐substituted derivatives. The global reactivity analysis showed that the electrophilicity index can be an indicator of electron‐injection capability in these complexes. Local reactivity analysis showed that atomic sites that are prone to nucleophilic/electrophilic attack are atoms C‐4 in L3/C‐5 in L1. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Homogeneous,unimolecular gas‐phase elimination kinetics of ethyl esters of glyoxylic, 2‐oxo‐propanoic,and 3‐methyl‐2‐oxo‐butanoic acids

The rates of elimination of several ethyl esters of 2‐oxo‐carboxylic acid were determined in a seasoned static reaction vessel over the temperature range 350–430°C and pressure range 33–240 Torr. The reactions, in the presence of a free‐radical inhibitor, are homogeneous, unimolecular, and follow a first‐order rate law. The overall and partial rate coefficients are expressed by the Arrhenius equation. Ethyl glyoxalate Ethyl 2‐oxo‐propionate Ethyl 3‐methyl‐2‐oxo‐butyrate The mechanisms of these elimination reactions are described in terms of concerted cyclic transition state structures. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 268–275, 2007     

Diastereoselective Electrophilic Amination of Chiral 1‐Benzoyl‐2,3,5,6‐tetrahydro‐3‐methyl‐2‐(1‐methylethyl)pyrimidin‐4(1H)‐one for the Asymmetric Syntheses of α‐Substituted α,β‐Diaminopropanoic Acids

The chiral compounds (R)‐ and (S)‐1‐benzoyl‐2,3,5,6‐tetrahydro‐3‐methyl‐2‐(1‐methylethyl)pyrimidin‐4(1H)‐one ((R)‐ and (S)‐ 1 ), derived from (R)‐ and (S)‐asparagine, respectively, were used as convenient starting materials for the preparation of the enantiomerically pure α‐alkylated (alkyl=Me, Et, Bn) α,β‐diamino acids (R)‐ and (S)‐ 11 – 13 . The chiral lithium enolates of (R)‐ and (S)‐ 1 were first alkylated, and the resulting diasteroisomeric products 5 – 7 were aminated with ‘di(tert‐butyl) azodicarboxylate’ (DBAD), giving rise to the diastereoisomerically pure (≥98%) compounds 8 – 10 . The target compounds (R)‐ and (S)‐ 11 – 13 could then be obtained in good yields and high purities by a hydrolysis/hydrogenolysis/hydrolysis sequence.     

A convenient synthesis of novel pyrido(1′,2′:1,2)imidazo[5,4‐d]‐1,2,3‐triazinones from imidazo[1,2‐a]pyridines

The imidazo[1,2‐a]pyridine system was investigated as a synthon for the building of very attractive fused triazines, a planar, angular tri‐heterocycle with potential biological activity. Thus ethyl 3‐nitroimidazo[1,2‐a]pyridine‐2‐carboxylate was treated with ammonia or with an excess of primary amines to generate the corresponding substituted nitro carboxamidoimidazopyridines. The nitro substituent in the latter products, was reduced to yield 3‐amino‐2‐carboxamidoimidazo[1,2‐a]pyridine derivatives, which in turn were treated with nitrous acid to furnish 1‐oxo‐2‐substituted pyrido(1′,2′:1,2)imidazo[5,4‐d]‐1,2,3‐triazines.     

Effects of alkyl groups in the rate determining step of the Baeyer-Villiger reaction of phenyl alkyl ketones: a quantum chemistry study

In this work, we have studied the substituent effect of several alkyl groups in the rate-determining step of the catalyzed Baeyer-Villiger (BV) reaction of phenyl alkyl ketones with performic (PFA) and trifluoroperacetic (TFPAA) acids, using quantum chemistry methods. Our results reveal that the substituent effect is more pronounced in the migration step barriers than in the corresponding addition step; that could change the rate-determining step (RDS) of the reaction, as observed in the oxidation of phenyl tert-butyl ketone with both peracids. In addition, the effect of the acid/peracid pairs used is also analyzed. We have demonstrated that the addition step is less susceptible to the acid/peracid nature since the acid strength and the nucleophilicity of the peracid have opposite effects. The effect of the acid/peracid pair is much more pronounced in the migration step because it only depends on the leaving ability of the acid, which in turn depends on its strength. These observations are relevant for understanding the effects of the substrate, the peracid, and the catalyst on the switching of the RDS in the BV reaction.     

Synthesis and Characterization of Sol-Gel Cu-ZrO2 and Fe-ZrO2 Catalysts

Fe-ZrO₂ and Cu-ZrO₂ xerogels were prepared by a sol-gel method. The effect of the hydrolysis catalyst during the gelation step, namely H₂SO₄ or NH₄OH, on the properties of the resulting materials was investigated by XRD, BET, TGA/DTA, TPD of ammonia, FTIR, and TPR. Fe-ZrO₂ and Cu-ZrO₂ xerogels, with sulfuric acid introduced as the hydrolysis catalyst, mainly crystallyzed in the tetragonal phase and exhibited larger surface area and acid amount than those obtained with NH₄OH. Ammonia TPD shows that copper promoted sulfated zirconia is the most acidic material. TGA and FTIR reveal that under oxidizing conditions sulfated zirconia promoted with iron and copper retains more sulfate species than unpromoted sulfated zirconia. Regardless of the hydrolysis catalyst employed, copper promoted catalysts calcined at 600°C, contain a large fraction of copper oxide specieseasily reduced at low temperatures. These copper oxide species are believed to have different environment and interactions with the surface oxygen vacancies of the zirconia support. A FeO-like phase appears to be the most probable one after reduction of Fe-ZrO₂ catalysts prepared with NH₄OH as the hydrolysis catalyst. The formation of Fe° species may be hindered by the high dispersion and interaction of Fe²⁺ ions with the zirconia support. On the other hand, the reduction peaks of iron oxide and sulfate species exhibit a considerable overlap in the TPR profiles of sulfated Fe-ZrO₂ samples. Hence, the nature of the supported phase in the latter samples is rather uncertain.     

Novel acid-catalyzed rearrangement of tetrahydro-1,2,3,4-tetrazines: unexpected formation of glycosazones

The present contribution discloses a simple and unexpected acid-catalyzed cleavage of tetrahydrotetrazines leading to 1,2-bis(hydrazones). Incorporation of a chiral fragment derived from carbohydrates enables the rapid preparation of glycosazones, a family of compounds employed by Emil Fischer to elucidate the configuration of sugars. In addition, a mechanistic proposal accounts for experimental observations.     

A high statistics measurement of the Lambda(+)(c) lifetime

A high statistics measurement of the Lambda(+)(c) lifetime from the Fermilab fixed-target FOCUS photoproduction experiment is presented. We describe the analysis technique with particular attention to the determination of the systematic uncertainty. The measured value of 204.6 +/- 3.4 (stat) +/- 2.5 (syst) fs from 8034 +/- 122 Lambda(+)(c)-->pK(-)pi(+) decays represents a significant improvement over the present world average.     

Delocalized quasiparticles in the vortex state of an overdoped high-T(c) superconductor probed by 63Cu NMR

We report the spin Knight shift (K(s)) and the nuclear spin-lattice relaxation rate (1/T1) in the vortex state as a function of magnetic field (H) up to 28 T in the high-Tc superconductor TlSr2CaCu2O6.8 (Tc = 68 K). At low temperatures well below Tc, both K(s) and 1/T1 measured around the middle point between the two nearest vortices (saddle point) increase substantially with increasing field, which indicate that the quasiparticle states with an ungapped spectrum are extended outside the vortex cores in a d-wave superconductor. The density of states (DOS) around the saddle point is found to be kappaN(0)square root[H/H(c2)], with kappa = 0.5-0.7 and N0 being the normal-state DOS.