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

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Abstract
Reaction of MgMeBr with [MCl2L2] and [MCl2(η-C5Me5)L][L =(2,6-Pri 2C6H3)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.