Intramolecular C−H Activation Reactions of Molybdenacyclobutanes

Molybdenacyclobutane complexes can be prepared by reaction of Cp*Mo(NO)(CHCMe₃) (formed spontaneously by loss of neopentane from Cp*Mo(NO)(CH₂CMe₃)₂ (1) under ambient conditions) with cyclic olefins, including cyclopentene, cycloheptene, and cyclooctene. The cyclopentene metallacyclobutane orients the metallacycle bridgehead protons cis to each other. A trans arrangement is observed for the cyclooctene congener, and both cis and trans orientations occur for the cycloheptene species. The reaction of 1 with cyclohexene initially forms a metallacyclobutane that then undergoes an allylic C−H activation to form an allyl−alkyl-coupled product with the concomitant loss of H₂. The analogous allyl−alkyl structure is also observed as the thermodynamic product for the reactions of cycloheptene and cyclooctene with 1. The cyclooctene allyl−alkyl compound (5C) can be converted to an η²-diene complex by heating with pyridine. Alternatively, heating of 5C in the presence of a variety of olefins displaces the diene ligand that can then be isolated in its unbound state.