Thermolysis of Cp'W(NO)(CH2CMe3)2 (1 ) [Cp' = (?5-C5Me4H)] at temperatures ranging from 70 �C to 120 �C results in the loss of neopentane and the formation of the 16e alkylidene intermediate complex, Cp'W(NO)(=CHCMe3), (A ). In the presence of aromatic hydrocarbons, 1  effects the a single C-H action of the solvent molecule to give 16e complexes of the form Cp'W(NO)(CH2CMe3)(?1-aryl). In solutions of aliphatic hydrocarbons 1  effects multiple C-H activations to produce 18e complexes of the form Cp'W(NO)(H)(?3-allyl), resulting from three successive C-H activations of the hydrocarbon substrate and the loss of the second neopentyl ligand. A series of mixed alkyl complexes Cp'W(NO)(CH2CMe3)R [R = CH2SiMe3, CH2CH3, CH3] has been synthesized to investigate the effect of changing one alkyl ligand on the C-H activation chemistry. Results of the thermolyses of these mixed alkyl complexes in various hydrocarbons will be presented.

Thermal chemistry of Cp'W(NO)(CH2CMe3)R complexes [Cp' = (η5-C5Me4H), R = CH2CMe3, CH2SiMe3, CH2CH3, CH3]

243rd National Meeting (2012)

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