Derivatives of Group 4 metal amide chlorides and fluorides: synthesis, structure and characterization of novel dimethyl and fluoro–chloro complexes

Abstract

Reaction of MgMeBr with [MCl₂L₂] and [MCl₂(η-C₅Me₅)L][L =(2,6-Prⁱ₂C₆H₃)N(SiMe₃), M = Zr or Hf] gave the corresponding dimethyl complexes [MMe₂L₂](M = Zr 1a or Hf 1b) and [MMe₂(η-C₅Me₅)L](M = Zr 2a or Hf 2b). Reaction of [ZrF₂L₂] with AlMe₃ also yielded 1a. The structures of 1a and 2a have been determined by single-crystal X-ray crystallography. Upon reaction of 1 molar equivalent of SnMe₃F with [MCl₂L₂] and [MCl₂(η-C₅Me₅)L] mixed fluoro–chloro complexes, [MCl(F)L₂](M = Zr 3a or Hf 3b) and [MCl(F)(η-C₅Me₅)L](M = Zr 4a or Hf 4b) were formed, via elimination of SnMe₃Cl. The structure of 4a has been determined by single-crystal X-ray analysis.