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)(NCMe2)(Ph2PCH2CH2PPh2)2][HSO4]

The first direct observation of oxidative addition of an oxime upon N–O bond cleavage has been reported in the reaction of Me2CNOH 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)(NCMe2)(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.