Data di Pubblicazione:
1977
Citazione:
Polynuclear Isocyanides Complexes of Rhenium / P. Romiti, M. Freni, G. D'Alfonso. - In: JOURNAL OF ORGANOMETALLIC CHEMISTRY. - ISSN 0022-328X. - 135:3(1977), pp. 345-349. [10.1016/S0022-328X(00)88086-9]
Abstract:
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.
Tipologia IRIS:
01 - Articolo su periodico
Elenco autori:
P. Romiti, M. Freni, G. D'Alfonso
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