Abstract

The dimethyl aryloxide complexes [(PNP)M(CH3)(2)-(OAr)] (M=Zr or Hf; PNP-=N[2-P(CHMe2)(2)-4-methylphenyl](2)); Ar=2,6-iPr(2)C(6)H(3)), which were readily prepared from [(PNP) M(CH3)(3)] by alcoholysis with HOAr, undergo photolytically induced alpha-hydrogen abstraction to cleanly produce complexes [(PNP) M=CH2(OAr)] with terminal methylidene ligands. These unique systems have been fully characterized, including the determination of a solid-state structure in the case of M-Zr.