Oracio Serrano

New seven membered palladacycles: C–Br bond activation of 2-bromo-pyridine derivative by Pd(II)

C-Br bond activation followed by a C-C coupling reaction of the 2-bromo-pyridyl unit of [1-phenyl-2-(6-bromopyridin-2-yl)-benzoimidazole] was performed by Pd(CH(2)CMe(2)-o-C(6)H(4))(η(4)-COD). Two new seven membered palladacycles were obtained. A combined experimental and theoretical DFT study elucidates the mechanism for this reaction.

Csp2–Br bond activation of Br-pyridine by neophylpalladacycle: formation of binuclear seven-membered palladacycle and bipyridine species

In this work, the synthesis and reactivity of seven-membered palladacycles are described, and a novel bi-pyridine synthesis in a catalytic pathway is reported. Neophyl-palladacycle(I) reacts with an excess of 2-Br-pyridine, giving the desired new binuclear seven-membered palladacycle (1) and unexpectedly, a bipyridine complex, [Pd(BiPy)Br2]. ESI-HRMS experiments show that fragmentation of the Pd–Br bond in 1 can take place producing unusual two coordinated Pd(II) molecular ions, [Pd(NeoPyR)]+.

Determination of copper and lead in tequila by conventional MALDI-TOFMS and partial least square regression

RATIONALE Quantification of small molecules by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) is challenging yet attractive, due to micro-scale procedural simplicity, high throughput and lack of memory effects. Since these features are important while analyzing trace elements in quality control schemes, MALDI-TOFMS was used for the determination of copper (Cu) and lead (Pb) in tequila with quantification carried out by partial least squares regression (PLS2) and by univariate calibration (UC). METHODS In the proposed procedure, Bi(III) was added as internal standard (IS), diethyldithiocarbamate complexes were formed (pH 7.4) and extracted into chloroform; after solvent evaporation and re-constitution in acetonitrile, the sample was co-crystallized with α-cyano-4-hydroxycinnamic acid on a steel target. From the acquired mass spectra, UC was performed using IS-normalized signals of the monoisotopic ions of analytes, and the m/z range 350-513 was used for PLS2. Accuracy was tested by recovery experiments and by inductively coupled plasma (ICP)-MS analysis. RESULTS When compared with direct analyte signal measurements, application of IS yielded enhanced analytical performance using either UC or PLS2; the method quantification limits were: 11.1 μg L-1 , 23.4 μg L-1 for Cu and 89.8 μg L-1 , 97.1 μg L-1 for Pb, respectively. In tequila, MALDI-TOFMS and ICP-MS provided consistent results for Cu (165-2599 μg L-1 ); Pb was not detected in any sample by MALDI-TOFMS, yet recoveries obtained after standard addition were indicative of acceptable accuracy (400 μg L-1 Pb added; recoveries: 91.2-108% for UC and 98.8-120% for PLS2). CONCLUSIONS New experimental evidence has been provided supporting the inclusion of trace metals quantification within a range of MALDI-TOFMS applications. Slightly better results were obtained for UC as compared with PLS2 yet both methods can be recommended for testing the compliance of Cu and Pb levels with Official Mexican Norm. Of note, while using PLS2, there is no need for signal integration nor for IS normalization.

Microwave-Assisted Synthesis and Characterization of [Rh2(OAc)4(L)2] Paddlewheel Complexes: A Joint Experimental and Computational Study

The synthesis of four rhodium(II) paddlewheel complexes bearing axial aromatic amines and coumarin ligands, with formula [Rh2(OAc)4(L)2] (L = NH2Mesityl (1), NH2Dip (2), NH2Couma (3), coumarin (4)), prompted by microwave irradiation, was carried out successfully. All of the complexes were characterized by the melting point, elemental analysis, NMR, IR, and UV/Visible spectroscopy. Additionally, the structure of complexes 1-2 and 4 was corroborated by single-crystal X-ray diffraction. Cyclic voltammetry, ESI-MS, and tandem MS analyses were carried out in compound 1 for gaining further insight into its stability. Finally, a DFT study shows that complexes 1–4 are the thermodynamic products, having as intermediates complexes 1′–4′ which, under our experimental conditions, cannot be isolated.