The pincer complex (PNN)RuH(CO), with a de-aromatized pyridine in the ligand backbone, is shown to react with nitriles in a metal-ligand cooperative manner. This leads to the formation of a series of complexes with new Ru-N(nitrile) and C(ligand)-C(nitrile) bonds. The initial nitrile cycloaddition products, the ketimido complexes 3, have a Brønsted basic (nitrile-derived) Ru-N fragment. This is able to deprotonate a CH side-arm of the pincer ligand to give ketimine complexes (4) with a de-aromatized pyridine backbone. Alternatively, the presence of a CH group adjacent to the nitrile functionality can lead to tautomerization to an enamido complex (5). Variable-temperature NMR studies and DFT calculations provide insight in the relative stability of these compounds and highlight the importance of their facile interconversion in the context of subsequent nitrile transformations.
The curing of bis-methacrylate–styrene resins initiated by the cobalt catalyzed decomposition of cumyl hydroperoxide is monitored at ambient temperatures in situ by EPR and Raman spectroscopy.
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