560133-91-7Relevant academic research and scientific papers
Synthesis and characterization of radical cations derived from mono- And biferrocenyl-substituted 2-Aza-1,3-butadienes: A study of the influence of an asymmetric and oxidizable bridge on intramolecular electron transfer
Lloveras, Vega,Caballero, Antonio,Tarraga, Alberto,Velasco, M. Desamparados,Espinosa, Arturo,Wurst, Klaus,Evans, David J.,Vidal-Gancedo, Jose,Rovira, Concepcio,Molina, Pedro,Veciana, Jaume
, p. 2436 - 2450 (2005)
The synthesis and study of structural and electronic properties of mono-ferrocenyl π-conjugated complexes 5a-d, whose electronic characteristics have been systematically varied by introducing an electron-donating or electron-withdrawing substituent either at the 1-position or at the 4-position of the 2-aza-1,3-butadiene moiety linked to the ferrocenyl unit, are presented. The structural and electronic properties of the homobimetallic complex 5f, with two ferrocene units linked through the asymmetric and oxidizable 2-aza-1,3-butadiene bridge, is also reported. The crystal structures of complexes 5b, 5d, and 5f show a large degree of conjugation in this family of compounds. Complexes 5 show a rich electrochemical behavior due both to the oxidation of ferrocenyl units and the 2-aza-1,3-butadiene bridge, as revealed by cyclic voltammetry. Radical cations 5+. were prepared from 5 by coulomet ric oxidations following their generation by absorption spectroscopy. The electronic properties of all reported neutral and oxidized π-conjugated complexes have been investigated by means of UV/Vis-near-IR, EPR and 57Fe Moessbauer spectroscopy. The detailed study of mono-oxidized species 5a+.-5f+. has permitted the determination of the influence of an asymmetric bridge with an electroactive character on the intramolecular electron transfer (IET) phenomenon, thus demonstrating that the 2-aza-1,3-butadiene bridge promotes the IET between the two metallic units of 5f+. through two different pathways. The experimental data and conclusions are supported by DFT computations (B3LYP/3-21G*) and time-dependent DFT methods. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
Aza-Wittig reaction of N-phosphorylalkyl phosphazenes with carbonyl compounds and phenylisocyanate. Synthesis of 4-amino-3-phosphoryl-2-azadienes and pyrazine-phosphonates
Palacios, Francisco,Ochoa De Retana, Ana María,Martínez De Marigorta, Eduardo,Rodriguez, Marta,Pagalday, Jaione
, p. 2617 - 2623 (2007/10/03)
Simple and functionalized N-phosphorylalkyl imines and N-phosphorylalkyl-N′-phenyl-carbodiimides are obtained by aza-Wittig reaction of phosphazenes derived from aminophosphonates with carbonyl compounds and phenyl isocyanate. The reaction with dimethylformamide diethyl acetal (DMF-DEA) of these functionalized imines leads to the synthesis of 4-amino-3-phosphoryl-2-azadienes. N-Phosphorylmethyl imine derived from benzaldehyde can be used for the preparation of substituted pyrrole-phosphonates, while acid treatment of 4-dimethylamino-3-diethylphosphoryl-1-phenyl-2-azadiene gives diethyl 5-diethylphosphorylpyrazin-2-ylphosphonate.
