Rearrangements and stereomutations of metallacycles derived from allenes and imidozirconium complexes

J Am Chem Soc. 2005 Feb 16;127(6):1752-64. doi: 10.1021/ja045607k.

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.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Alkadienes / chemistry*
  • Catalysis
  • Circular Dichroism
  • Crystallography, X-Ray
  • Cyclization
  • Cyclobutanes / chemical synthesis*
  • Cyclobutanes / chemistry
  • Kinetics
  • Organometallic Compounds / chemistry*
  • Spectrophotometry, Ultraviolet
  • Stereoisomerism
  • Thermodynamics
  • Zirconium / chemistry*

Substances

  • Alkadienes
  • Cyclobutanes
  • Organometallic Compounds
  • propadiene
  • Zirconium