The kinetics of the decomposition of MeTl(OA)2 in C5D5N, and in the presence of equimolar amounts of C5D5N in CD3OD, have been studied by 1H NMR-spectroscopy. Products in pyridine are TlOAc and N-methylpyridinium acetate, as well as MeOac and decomposition products of N-methylpyridinium acetate; the reaction order changes during decomposition. In methanol MeTl(OAc)2 and pyridine give>90 mole-% N-methylpyridinium acetate and <10 mole-% MeOAc; the reaction follows in good approximation a second order law. On the basis of data calculated from the derived rate equation and experimental data, a bimolecular mechanism, and, as rate determining ste, an SN 2-attack of pyridine and OAc- at the Tl-bonded CH3-group of MeTlOAc+ is formulated. Because of the less nucleophilic character of OAc- in comparison with pyridine, MeOAc is formed only in minor amounts.
|Titolo:||Polynuclear Isocyanides Complexes of Rhenium|
D'ALFONSO, GIUSEPPE (Ultimo)
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
|Data di pubblicazione:||1977|
|Digital Object Identifier (DOI):||10.1016/S0022-328X(00)88086-9|
|Appare nelle tipologie:||01 - Articolo su periodico|