THE FIRST DIRECT OBSERVATION OF N-O BOND-CLEAVAGE IN THE OXIDATIVE ADDITION OF AN OXIME TO A METAL CENTER - SYNTHESIS AND CRYSTAL-STRUCTUREOF THE METHYLENEAMIDE COMPLEX TRANS-[RE(OH)(N=CME2)(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 Me2C=NOH with tra ns-[ReCl(N-2)(Ph2PCH2CH2PPh2)(2)] in the presence of Tl[BF4]-Tl[HSO4], to form, in a single-pot experiment, the methyleneamide complexes tra ns-[Re(OH)(N=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 pi acceptor and exerts a significant trans in fluence on the hydroxide ligand.