1. Introduction In spite of the interesting performances that MoCl5, 1, exhibits in catalysis, its reactivity with limited amounts of organic reactants is still far from being well elucidated . A better knowledge of this chemistry may help the understanding and, hopefully, the improvement of catalytic processes. This is particularly true on considering that the catalytic activity of 1 is often reported to be associated with the presence of an “oxygen modifier” (e.g. ether, amide) acting as promoter . 2. Results and Discussion Compound 1 reacts with a two-fold excess of the amide MeCONHPh in chlorinated solvent, affording selectively the acylamidinium complex [MoOCl4MeC(O)N(Ph)C(Me)NHPh], 2. The reaction appears to proceed with oxygen-chlorine exchange between the metal centre and one amide unit, followed by CN coupling involving the resulting chloroiminium cation [C(Me)(Cl)=NHPh]+ and another amide molecule. Differently, the 1:2 reaction of 1 with the N-disubstituted HCONMe2 (dmf) stops at the formation of the iminium containing salt [CH(Cl)=NMe2][MoOCl4(dmf)], 3. The X-Ray structures of 2 and 3 have been determined (see Figure).
|Titolo:||UNPRECEDENTED AMIDE DIMERIZATION VIA C-N COUPLING PROMOTED BY MOLYBDENUM PENTACHLORIDE AT ROOM TEMPERATURE|
|Anno del prodotto:||2010|
|Appare nelle tipologie:||4.3 Poster|