Metal-mediated formation of C-O bonds is a central transformation to strategies for selective hydrocarbon oxidation. Despite this, there are few complexes that have been reported to undergo well-defined oxygen atom insertion into metal-hydrocarbyl bonds. This presentation is focused on the study of oxygen atom insertion into the W-C bond of Cp*W(O)2(CH2SiMe3) with several oxidants via different mechanisms, based on combined experimental and computational studies. It is likely that an organometallic Baeyer-Villiger (OMBV) transition state is more favorable for the oxy-insertion with NaIO4 while the oxy-insertion with H2O2 in the presence of NaOH likely has a peroxo transition state through a Cp*WO(?2-O2)(CH2SiMe3) intermediate.

Variable pathways for oxygen atom insertion into metal-carbon bonds: The case of Cp*W(O)2(CH2SiMe3)

244th National Meeting (2012)

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