Palladium(0)-catalyzed trimerization of arylisocyanates into 1,3,5-triarylisocyanurates in the presence of diimines: a nonintuitive mechanism.
2007
We show here that palladium(0) (dibenzylideneacetone) complexes bearing 1,10-phenanthroline constitute efficient catalysts for the cyclotrimerization of aromatic isocyanates. For the first time, the mechanism of this reaction has been investigated experimentally and theoretically with group 10 catalysts. This investigation provides a very consistent picture of the catalytic cycle. Notably, we establish that the reaction does not proceed by stepwise cycloadditions or ring insertions involving metallacyclic intermediates, as might have been anticipated. Rather, in our proposal, the initial steps of the mechanism resemble the chain-growth process operative during the anionic polymerization of isocyanates and feature charge-separated intermediates. These steps are then followed by ring closure on the metal center of the last intermediate formed to yield a seven-membered metallacycle that reductively eliminates the cyclotrimer and re-forms the active species. In addition, we conclusively show that the (known) ...
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