%0 Generic %A Michael, Forrest E. %A Duncan, Andrew P. %A Sweeney, Zachary K. %A Bergman, Robert G. %D 2005 %T Rearrangements and Stereomutations of Metallacycles Derived from Allenes and Imidozirconium Complexes %U https://acs.figshare.com/articles/dataset/Rearrangements_and_Stereomutations_of_Metallacycles_Derived_from_Allenes_and_Imidozirconium_Complexes/3301021 %R 10.1021/ja045607k.s004 %2 https://ndownloader.figshare.com/files/5138755 %K bond homolysis %K Imidozirconium Complexes %K Metallacycles Derived %K monoazadiene complexes %K room temperature %K diarylallenes racemize %K imidozirconium complexes %X The mechanisms of the rearrangements and stereoinversion of azametallacyclobutenes generated via [2+2] cycloaddition of allenes and imidozirconium complexes have been studied. Metallacycles derived from allenes bearing β-hydrogen atoms racemize at room temperature by reversible β-hydride elimination, a process which is also responsible for their eventual conversion to monoazadiene complexes. Metallacycles derived from diarylallenes racemize by reversible thermal bond homolysis at 95 °C; racemization of these metallacycles is also catalyzed by mild oxidants. %I ACS Publications