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

Linda E. Eijsink, Sébastien C. P. Perdriau, Johannes G. de Vries, Edwin Otten

Research output: Contribution to journalArticleAcademicpeer-review

25 Citations (Scopus)
198 Downloads (Pure)

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.

Original languageEnglish
Pages (from-to)16033-16039
Number of pages7
JournalDalton Transactions
Volume45
Issue number40
DOIs
Publication statusPublished - 2016

Keywords

  • BOND ACTIVATION
  • CO2
  • HYDROGENATION
  • CATALYSIS
  • ACCEPTORS
  • BINDING
  • DESIGN

Cite this