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Rearrangements and stereomutations of metallacycles derived from allenes and imidozirconium complexes
Forrest E Michael1, Andrew P Duncan, Zachary K Sweeney
1Department of Chemistry, University of California, Berkeley, CA 94720, USA.
Abstract:
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 beta-hydrogen atoms racemize at room temperature by reversible beta-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 degrees C; racemization of these metallacycles is also catalyzed by mild oxidants.
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