Parallel Transformations of Cyclohexene Mediated by the Cp*W(NO) Fragment

Hydrogenolysis of Cp*W(NO)(CH2CMe3)2 at room temperature in cyclohexene results in the formation of the intermediate 16e organometallic complex, [Cp*W(NO)(η2-cyclohexene)]. This intermediate leads to three parallel transformations of cyclohexene, namely (a) C−H activation of cyclohexene to form an η3-cyclohexenyl hydrido complex, (b) combination of cyclohexene and H2 to form a cyclohexyl hydrido complex, and (c) coupling of two molecules of cyclohexene with concomitant loss of two hydrogen atoms to form a complex containing a novel η,η3-(cyclohexyl)cyclohexenyl ligand. Single-crystal X-ray crystallographic analyses of products resulting from transformations (b) and (c) have been effected.