Alkylideneamido-derivatives of metals and metalloids. Part V. Complexes of the late transition metals with (CF3)2C:N? as ligand, and a tautomeric hydrogen transfer from metal to ligand

Abstract

Reaction of LiN:C(CF3)2 or Me3SnN:C(CF3)2 with a PtII, RhI, or IrI halide generally leads to the appropriate d8 metal alkylideneamide (reactivity: Li > Me3Sn). A PtII derivative, trans-Pt[N:C(CF3)2](SnMe3)(PPh3)2 is also obtained by an oxidative addition of Me3SnN:C(CF3)2 to Pt(PPh3)2(stilbene). trans-Pt(H or D)[N:C(CF3)2](PPh3)2 rearranges into Pt[H(D)N:C(CF3)2](PPh3)2 by heating with PPh3 under reflux in benzene, or without phosphine in boiling xylene. The latter isomer reacts with an excess of PPh3 to give Pt[HN:C(CF3)2](PPh3)3. The spectra of the new thermally- and hydrolytically-stable compounds, as well as the M–N cleavage by HCl, are discussed.