β-Hydride- or β-Methide-Bearing Alkyl Complexes

In the course of study into the stability and reactivity of early transition metal (TM) complexes, it has been further confirmed that the pentamethylcyclopentadienyl acetamidinate ligand set is particularly apt for the stabilization of early TM-alkyl species. The first examples of a solid state structure of cyclobutylmethyl complexes were obtained, after pentamethylcyclopentadienylacetamidinatezirconium (Cp*ZA) cyclobutylmethyl compounds were prepared via hydrozirconation of methylenecyclobutane. The ring opening of neutral and cationic cyclobutylmethyl Cp*ZAs and the conformation of the product pendant olefin pentenyl cation were studied via selective neuclear Overhouser effect (nOe) confirming that the pendant olefin was coordinated to the cationic Zr center. To further study the properties of pendant olefin complexes, a methyl butenyl Cp*ZA complex was prepared, and was observed to convert to a Cp*ZA butadiene complex, presumably via a β-H abstraction by the metal-based methyl group. The reactivity of the first known non-base stabilized η2-styrene zirconiu