Monday, October 16, 2017

organic chemistry - Do eta-4 benzene ligands participate in Diels Alder or other cycloadditions?


While refreshing myself on denticity to answer another question, I started to read about hapticity, which is the coordination of a ligand through multiple continuous atoms. A famous case is ferrocene (bis[$\eta^5$-cyclopentadienyl]iron, $\ce{Cp2Fe}$), where all five carbon atoms in each cyclopentadienyl ligand (Cp) are coordinated to the iron center.


Benzene can also be a polyhaptic ligand, forming $\eta^4$ or $\eta^6$ complexes depending on the oxidation state of the metal. In particular, bis(benzene)ruthenium complexes can undergo redox shuttling, where one benzene ligand switches between $\eta^4$ and $\eta^6$.


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In the $\eta^4$ complex on the right, the top benzene ligand is now bent out of planarity, implying a break of aromaticity. This compound looks like a good dienophile for a Diels-Alder reaction. The article linked in the Wikipedia page on this switching phenomenon is published in Angewandte Chemie, International Edition, which is behind a paywall for me.



Does coordination of benzene to a metal in the $\eta^4$ mode activate it toward cycloadditions? Because of paywalls, I would appreciate summaries of articles in addition to links to them. My attempts to find articles using Google Scholar led me to articles about the construction of benzenes by metal mediated cycloadditions, and not to reactions of benzene itself.






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