Amido-derivatives of metals and metalloids. Part VI. Reactions of titanium(IV), zirconium(IV), and hafnium(IV) amides with protic compounds

Abstract

The reactions of metal (Ti, Zr, or Hf) dialkylamides with acidic hydrocarbons (such as C₅H₆), hexamethyldisilazane, alcohols, and thiols are reported. In this way, numerous π-organometallic derivatives, such as CpTi(NMe₂)₃ and (π-C₅H₅)₂Zr(NMe₂)₂, silylamides, alkoxides, and thiolates have been prepared. Noteworthy are (a) differences (possibly steric in origin), with regard to the number of groups displaced, between Ti amides and amides of either Zr or Hf, (b) the displacement order NR₂ > SR > Cp ≫ OR, and (c) the monomeric nature of all the products. Reactions between decaborane and either Ti(NMe₂)₄ or Me₃SnNMe₂ afforded Ti(NMe₂)₄,2B₁₀H₁₄ and Me₃SnNMe₂,B₁₀H₁₄, which are probably best formulated as [Ti(NMe₂)₂]²⁺[B₁₀H₁₃,Me₂NH]₂^– and [Me₃Sn]⁺[B₁₀H₁₃,Me₂NH]^–, respectively.