Ti-catalyzed homolytic opening of ozonides: a sustainable C-C bond-forming reaction

The unprecedented homolytic opening of ozonides promoted and catalyzed by titanocene(III) is reported. This novel reaction proceeds at room temperature under neutral, mild conditions compatible with many functional groups and provides carbon radicals suitable to form C-C bonds via both homocoupling and cross-coupling processes. The procedure has been advantageously exploited for the straightforward synthesis of the natural product brittonin A.     

Impact of the analytical blank in the uncertainty evaluation of the copper content in waters by flame atomic absorption spectrometry

Chemical analysts use analytical blanks in their analyses, but seldom is this source of uncertainty evaluated. Generally, there is great confusion. Although the numerical value of the blank, in some situations, can be negligible, its source of uncertainty cannot be. This article discusses the uncertainty contribution of the analytical blank using a numerical example of the copper content in waters by flame atomic absorption spectrometry. The results indicate that the uncertainties of the analytical blank can contribute up to 50% when the blank sample is considered in this analysis, confirming its high impact. This effect can be primarily observed where the analyte concentration approaches the lower range of the analytical curve. Even so, the blank is not always computed. Therefore, the relevance of the analytical blank can be confirmed by uncertainty evaluation.     

Theoretical study of methoxy group influence in the gas‐phase elimination kinetics of methoxyalkyl chlorides

The unimolecular gas‐phase elimination kinetics of 2‐methoxy‐1‐chloroethane, 3‐methoxy‐1‐chloropropane, and 4‐methoxyl‐1‐chloroburane has been studied by using density functional theory (DFT) methods to propose the most reasonable mechanisms of decomposition of the aforementioned compounds. Calculation results of 2‐methoxy‐1‐chloroethane and 3‐methoxy‐1‐chloropropane suggest dehydrochlorination through a concerted nonsynchronous four‐centered cyclic transition state (TS) to give the corresponding olefin. In the case of 4‐methoxyl‐1‐chloroburane, in addition to the 1,2‐elimination mechanism, the anchimeric assistance by the methoxy group, through a polar five‐centered cyclic TS, provides additional pathways to give 4‐methoxy‐butene, tetrahydrofuran and chloromethane. The bond polarization of the C? Cl, in the direction of C^δ+ ··· Cl^δ?, is the limiting step of these elimination reactions. The significant increase in rate together with the formation of a cyclic product tetrahydrofuran in the gas‐phase elimination of 4‐methoxyl‐1‐chloroburane is attributed to neighboring group participation of the oxygen of the methoxy group in the TS. The theoretical calculations show a good agreement with the reported experimental results. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Unusual nonoctahedral geometry with molybdenum oxoimido complexes containing η2-pyrazolate ligands

The preparation and oxygen-atom-transfer (OAT) reactivity of oxoimido complexes [MoO(N-t-Bu)(t-Bu(2)-4-Rpz)(2)] [where R = H (1), Br (2), and Me (3); t-Bu(2)pz = 3,5-di-tert-butylpyrazolate] are reported. The reaction of the potassium salt of the respective pyrazolate ligands and the molybdenum oxoimido precursor, [MoO(N-t-Bu)Cl(2)(dme)] (dme = dimethoxyethane), in toluene afforded complexes 1-3 in good yields. The complexes were fully characterized by (1)H and (13)C NMR and IR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray crystallography. The solid-state structures reveal that, in each case, the molybdenum center is coordinated by one oxo, one N-t-Bu group, and two sterically demanding pyrazolate ligands via their two adjacent nitrogen atoms in an η(2) fashion. Coordination around the metal center is severely distorted from octahedral and might be seen as closely approaching a distorted trigonal-prismatic geometry, which is relevant to the active site of dimethyl sulfoxide reductase in its oxidized form. The potential utility of all of the complexes 1-3 for OAT reactivity toward PMe(3) at room temperature is examined, and plausible mechanistic pathways are explored by density functional theory calculations. Furthermore, the complexes reported here open a new and convenient entry into mixed oxoimidomolybdenum complexes.     

Unexpected acidity enhancement triggered by AlH3 association to phosphines

The complexes formed by the interaction between a series of phosphines R-PH(2) (R = H, CH(3), c-C(3)H(5), C(6)H(5)) and AlH(3) have been investigated through the use of high-level G4 ab initio calculations. These very stable complexes behave as much stronger acids than the isolated phosphines. This dramatic acidity enhancement, which can be as high as 174 kJ mol(-1), results from a much greater stabilization of the anionic deprotonated species with respect to the neutral one, upon AlH(3) association. This effect depends quantitatively on the nature of the substituent R and is smaller for R = C(6)H(5) because of the conjugation of the P lone pair with the aromatic system. More unexpectedly, however, the phosphine-alane complexes, RPH(2):AlH(3), are more acidic than the corresponding phosphine-borane RPH(2):BH(3) analogues. This unexpected result is due to the enhanced stability of the anionic deprotonated species for complexes involving AlH(3), because the delocalization of the newly created P lone pair with the P-Al bonding density is more favorable when the Lewis acid is aluminum trihydride than when it is borane.     

Substituent effects on the thermochemistry of thiophenes. a theoretical (G3(MP2)//B3LYP and G3) study

Very good linear correlations between experimental and calculated enthalpies of formation in the gas phase (G3(MP2)//B3LYP and G3) for 48 thiophene derivatives have been obtained. These correlations permit a correction of the calculated enthalpies of formation in order to estimate more reliable "experimental" values for the enthalpies of formation of substituted thiophenes, check the reliability of experimental measurements, and also predict the enthalpies of formation of new thiophenes that are not available in the literature. Moreover, the difference between the enthalpies of formation of isomeric thiophenes with the same substituent in positions 2 and 3 of the ring has been analyzed. Likewise, a comparison of the substituent effect in the thiophene and benzene rings has been established.     

Comment on “Heteroclinic orbits in Chen circuit with time delay” [Commun. Nonlinear Sci. Numer. Simulat. 15 (2010) 3058–3066]

The authors claim in the abstract of the referenced paper that Existence of Shil’nikov type of heteroclinic orbit in Chen circuit with direct time delay feedback is proved using the undetermined coefficient method. As a result, Shil’nikov criterion guarantees that the circuit has Smale horseshoes and the circuit demonstrates chaos in a rigorous analytical sense. Unfortunately, we show in this comment that their demonstration is incorrect.     

Variable neighborhood search with ejection chains for the antibandwidth problem

In this paper, we address the optimization problem arising in some practical applications in which we want to maximize the minimum difference between the labels of adjacent elements. For example, in the context of location models, the elements can represent sensitive facilities or chemicals and their labels locations, and the objective is to locate (label) them in a way that avoids placing some of them too close together (since it can be risky). This optimization problem is referred to as the antibandwidth maximization problem (AMP) and, modeled in terms of graphs, consists of labeling the vertices with different integers or labels such that the minimum difference between the labels of adjacent vertices is maximized. This optimization problem is the dual of the well-known bandwidth problem and it is also known as the separation problem or directly as the dual bandwidth problem. In this paper, we first review the previous methods for the AMP and then propose a heuristic algorithm based on the variable neighborhood search methodology to obtain high quality solutions. One of our neighborhoods implements ejection chains which have been successfully applied in the context of tabu search. Our extensive experimentation with 236 previously reported instances shows that the proposed procedure outperforms existing methods in terms of solution quality.     

Two-sex Branching Models with Random Control on the Number of Progenitor Couples

In this paper we introduce a class of two-sex branching models where, in each generation, a random control on the number of progenitor couples in the population is considered. For such a class, several probabilistic results are established. Also assuming offspring probability distribution belonging to the bivariate power series family, Bayes estimators for the mean vector and the covariance matrix of the offspring distribution are proposed. A computational method to determine highest posterior density credibility sets is stated. As illustration, a simulated example is provided.     

Weak crossed biproducts and weak projections

In this paper, we present the general theory and universal properties of weak crossed biproducts. We prove that every weak projection of weak bialgebras induces one of these weak crossed structures. Finally, we compute explicitly the weak crossed biproduct associated with a groupoid that admits an exact factorization.