Lanthanide(III) nitrobenzenesulfonates as new nitration catalysts: The role of the metal and of the counterion in the catalytic efficiency

Lanthanide(III) complexes of p-nitrobenzenesulfonic acid, Ln(p-NBSA)(3), m-nitrobenzenesulfonic acid, Ln(m-NBSA)(3), and 2,4-nitrobenzenesulfonic acid, Ln(2,4-NBSA)(3), were prepared, characterized and examined as catalyst for the nitration of benzene, toluene, xylenes, naphthalene, bromobenzene and chlorobenzene. The initial screening of the catalysts showed that lanthanum(III) complexes were more effective than the corresponding ytterbium(III) complexes, and that catalysts containing the bulky 2,4-NBSA ligand were less effective than the catalyst containing p-NBSA (nosylate) or m-NBSA ligands. Examination of a series of Ln(p-NBSA)(3) and Ln(m-NBSA)(3) catalysts revealed that there is a clear correlation between the ionic radii of the lanthanide(III) ions and the yields of nitration, with the lighter lanthanides being more effective. The X-ray single crystal structure of Yb(m-NBSA)(3).6H(2)O shows that two m-NBSA ligands are directly bound to the metal centre while the third ligand is not located in the first coordination sphere, but it is hydrogen bonded to one of the water molecules which is coordinated to ytterbium(III). NMR studies suggest that this structure is preserved under the conditions used in the nitration reaction. The structure of Yb(m-NBSA)(3) is markedly different from the structure of the well-known ytterbium(III) triflate catalyst. The coordination of the nitrobenzenesulfonate counterion to the lanthanide(III) ion suggests that steric effects might play an important role in determining the efficiency of these novel nitration catalysts. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

On sea level change in the North Sea influenced by the North Atlantic Oscillation: local and remote steric effects

In this study, contributions of both local steric and remote baroclinic effects (i.e., steric variations external to the region of interest) to the inter-annual variability of winter sea level in the North Sea, with respect to the North Atlantic Oscillation (NAO), for the period of 1953–2010 are investigated. On inter-annual time scales in this period, the NAO is significantly correlated to sea level variations in the North Sea only in the winter months (December–March), while its correlation to sea temperature over much of the North Sea is only significant in January and February. The discrepancy in sea level between observations and barotropic tide and surge models forced by tides and local atmospheric forcing, i.e., local atmospheric pressure effects and winds, in the present study are found to be consistent with previous studies. In the North Sea, local thermosteric effects caused by thermal expansion play a minor role on winter-mean NAO related sea level variability compared with atmospheric forcing. This is particularly true in the southeastern North Sea where water depths are mostly less than 25 m. Our calculations demonstrate that the discrepancy can be mostly explained by remote baroclinic effects, which appear as water mass exchanges on the continental shelf and are therefore only apparent in ocean bottom pressure. In the North Sea, NAO related sea level variations seem to be a hybrid of barotropic and baroclinic processes. Hence, they can only be adequately modelled with three-dimensional baroclinic ocean models that include contributions of baroclinic effects and large-scale atmospheric forcing external to the region of interest.