Amido-derivatives of metals and metalloids. Part X. Reactions of titanium(IV), zirconium(IV), and hafnium(IV) amides with unsaturated substrates, and some related experiments with amides of boron, silicon, germanium, and tin(IV)

Abstract

Insertion reactions of amides LM–(NR₂)_n with the dipoles AB to give the adducts LM(NR₂)_{n – x}(A–B–NR₂)_x are described. The amides included the Group IVA [M(NMe₂)₄(M = Ti, Zr, or Hf)] and IVB [Me₃M·NMe₂(M = Si, Ge, or Sn)] compounds and o-C₆H₄O₂B·NEt₂, while the dipoles were PhNCO, PhNCS, MeNCS, p-MeC₆H₄·N:C:N·C₆H₄Me-p, C₆H₁₁·N:C:N·C₆H₁₁, MeO₂C·C:C·CO₂Me, CO₂, CS₂, CH₂:CH·CN, PhCN, p-MeC₆H₄·CN, CH₂:CCl(CN), C₆F₅·CN, CCl₃·CN, [graphic omitted] and MeCH:CH·CHO. The problems discussed are the stoicheiometry of the reaction, the structure of the adducts, and the relative reactivities of the various amides and dipoles.