Abstract

Treatment of [TaCl2(CH3)(3)] with 2 equiv of NaOAr' (OAr' = 2,6-bis(diphenylmethyl)-4-tert-butylphenoxide) yields cleanly the bis-aryloxide trimethyl complex [(Ar'O)(2)Ta(CH3)(3)] (1), which is isolated in 92% yield and is spectroscopically and structurally characterized. Addition of 2 equiv of HOAr' to [TaCl2(CH3)(3)] results in clean protonation concurrent with formation of the bis-aryloxide methyl derivative [(Ar'O)(2)Ta(CH3)Cl-2] (2), which was also fully characterized, including an X-ray structure. Despite being close derivatives, complex 1 (trigonal bipyramidal) and 2 (square pyramidal) possess very different structures, with the e set in a square-pyramidal molecular orbital diagram being key to their preferred geometry. Addition of excess ylide, H2CPPh3, to 2 results in formation of the terminal tantalum methylidene chloride complex [(Ar'O)(2)Ta=CH2(Cl)(H2CPPh3)] (3) in 64% yield, which is characterized by multinuclear NMR spectroscopy and a solid-state structure determination.