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Issue 40, 2016
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Metal–ligand cooperative activation of nitriles by a ruthenium complex with a de-aromatized PNN pincer ligand

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Abstract

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 CH2 side-arm of the pincer ligand to give ketimine complexes (4) with a de-aromatized pyridine backbone. Alternatively, the presence of a CH2 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.

Graphical abstract: Metal–ligand cooperative activation of nitriles by a ruthenium complex with a de-aromatized PNN pincer ligand

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Supplementary files

Article information


Submitted
20 Jun 2016
Accepted
25 Aug 2016
First published
25 Aug 2016

This article is Open Access

Dalton Trans., 2016,45, 16033-16039
Article type
Paper

Metal–ligand cooperative activation of nitriles by a ruthenium complex with a de-aromatized PNN pincer ligand

L. E. Eijsink, S. C. P. Perdriau, J. G. de Vries and E. Otten, Dalton Trans., 2016, 45, 16033
DOI: 10.1039/C6DT02478E

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