Palladium(II) complexes with a phosphino-oxime ligand: synthesis, structure and applications to the catalytic rearrangement and dehydration of aldoximes

The treatment of [PdCl2(COD)] (COD = 1,5-cyclooctadiene) with 1 and 2 equivalents of 2-(diphenylphosphino)benzaldehyde oxime in dichloromethane at room temperature led to the selective formation of [PdCl2{κ2-(P,N)-2-Ph2PC6H4CH[double bond, length as m-dash]NOH}] (1) and [Pd{κ2-(P,N)-2-Ph2PC6H4CH[double bond, length as m-dash]NOH}2][Cl]2 (2), respectively, which represent the first examples of Pd(II) complexes containing a phosphino-oxime ligand. These compounds, whose structures were fully confirmed by X-ray diffraction methods, were active in the catalytic rearrangement of aldoximes. In particular, using 5 mol% complex 1, a large variety of aldoximes could be cleanly converted into the corresponding primary amides at 100 °C, employing water as solvent and without the assistance of any cocatalyst. Palladium nanoparticles are the active species in the rearrangement process. In addition, when the same reactions were performed employing acetonitrile as solvent, selective dehydration of the aldoximes to form the respective nitriles was observed. For comparative purposes, the catalytic behaviour of an oxime-derived palladacyclic complex has also been briefly evaluated.

An approach for characterising the weathering behaviour of Flysch slopes applied to the carbonatic Flysch of Alicante (Spain)

Various studies indicate that most of the slope instabilities affecting Flysch heterogeneous rock masses are related to differential weathering of the lithologies that make up the slope. Therefore, the weathering characteristics of the intact rock are of great importance for the study of these types of slopes and their associated instability processes. The main aim of this study is to characterise the weathering properties of the different lithologies outcropping in the carbonatic Flysch of Alicante (Spain), in order to understand the effects of environmental weathering on them, following slope excavation. To this end, 151 strata samples obtained from 11 different slopes, 5–40 years old, were studied. The lithologies were identified and their mechanical characteristics obtained using field and laboratory tests. Additionally, the slaking properties of intact rocks were determined, and a classification system proposed based on the first and fifth slake cycles (Id1 and Id5 respectively) and an Index of Weathering (IW5), defined in the study. Information obtained from the laboratory and the field was used to characterise the weathering behaviour of the rocks. Furthermore, the slaking properties determined from laboratory tests were related to the in-situ weathering properties of rocks (i.e., the weathering profile, patterns and length, and weathering rate). The proposed relationship between laboratory test results, field data, and in-situ observations provides a useful tool for predicting the response of slopes to weathering after excavation during the preliminary stages of design.