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DOI: 10.1039/A707213I (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 325-326

The first direct observation of N–O bond cleavage in the oxidative addition of an oxime to a metal centre. Synthesis and crystal structure of the methyleneamide complex trans-[Re(OH)(N[double bond, length half m-dash]CMe2)(Ph2PCH2CH2PPh2)2][HSO4]

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Cristina M. P. Ferreira, M. Fátima C. Guedes da Silva, Vadim Yu. Kukushkin, João J. R. Fraústo da Silva and Armando J. L. Pombeiro

Abstract

The first direct observation of oxidative addition of an oxime upon N–O bond cleavage has been reported in the reaction of Me2C[double bond, length half m-dash]NOH with trans-[ReCl(N2)(Ph2PCH2CH2PPh2)2] in the presence of Tl[BF4]–Tl[HSO4], to form, in a single-pot experiment, the methyleneamide complexes trans-[Re(OH)(N[double bond, length half m-dash]CMe2)(dppe)2][A] (A = BF4 1a or HSO4 1b) which undergo ready replacement of hydroxide by fluoride upon reaction with HBF4; X-ray crystallography (1b) showed that the linearly bound methyleneamide behaves as an effective π acceptor and exerts a significant trans influence on the hydroxide ligand.

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