The [2+2+2] cycloaddition reaction has become an invaluable tool for the synthetic chemistry in recent years, due to the increase of complexity of the accessed target molecules by this methodology. Over several decades, the members of group 9 of the periodic table have contributed significantly to the development and understanding of this particular cycloaddition reaction. On the other hand, catalyst complexes containing alkenes as ligands are widely used today as either catalysts or as precursor molecules for the facile generation of catalytically active metal species. In this tutorial review we want to describe the catalytically relevant chemistry of group 9 metal-alkene complexes and compile some recent applications in [2+2+2] cycloaddition reactions.
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