ABSTRACT
In order to design magnetically active molecular materials, it is desirable to arrange paramagnetic molecules in one dimension, which may lead to a molecular bar magnet. For this purpose, vanadocenyl units with three unpaired electrons each can be stacked in a head-to-head fashion. The target compound in this work is 1,8-bisvanadocenyl naphthalene, where the naphthalene backbone serves as a clamp keeping two vanadocene units together. The target compound in this work is obtained through the reaction of the disodium salt of 1,8-biscyclopentadiendiylnaphthalene with the cyclopentadienyl vanadium (CpV) transfer reagent [V(µ2-Cl)(η5-Cp)(thf)]2. The 1,8-bisvanadocenyl naphthalene is fully characterized. In addition, variable temperature 1H NMR spectroscopy, X-ray structure analysis, magnetic measurements and DFT calculations have been performed. In both experiment and theory, a weak antiferromagnetic coupling between the spin centers is found, with the spin highly localized on the V(ii) ions.
ABSTRACT
Methyldioxorhenium (MDO)-catalyzed C-O bond cleavage of a variety of lignin ß-O-4-model compounds yields phenolic and aldehydic compounds in homogeneous phase under mild reaction conditions. MDO is in situ generated by reduction of methyltrioxorhenium (MTO) and is remarkably stable under the applied reaction conditions allowing its reuse for least five times without significant activity loss. Based on the observed and isolated intermediates, 17 O- and 2 H-isotope labeling experiments, DFT calculations, and several spectroscopic studies, a reaction mechanism is proposed.
