Amido-derivatives of metals and metalloids. Part VI. Reactions of titanium(IV), zirconium(IV), and hafnium(IV) amides with protic compounds
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.
- This article is part of the themed collection: A collection of papers in memory of Professor Michael Lappert