Lutidine-derived Ru-CNC hydrogenation pincer catalysts with versatile coordination properties

Journal article (2014)

Authors

G.A. Filonenko Eindhoven University of Technology

Elena Cosimi DSM

Laurent Lefort DSM

Matthew P. Conley ETH Zürich

Christophe Copéret ETH Zürich

M Lutz Universiteit Utrecht

Emiel J.M. Hensen Eindhoven University of Technology

E.A. Pidko Eindhoven University of Technology

Affiliation

External organisation

Hydrogenation Ruthenium N-heterocyclic carbene Metal-ligand cooperation Nitrile activation

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Published Date

2014

Language

English

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Abstract

Lutidine-derived bis-N-heterocyclic carbene (NHC) ruthenium CNC-pincer complexes (Ru-CNC's) were prepared. Depending on the synthetic procedure, normal (1, 2) or mixed normal/abnormal NHC-complexes (3) are formed. In the presence of phosphazene base, Ru-CNC complexes activate nitriles to give ketimino compounds 4-6. Nitrile adduct 4 shows reactivity toward strong bases to yield dearomatized complex 7, which heterolytically activates H₂ to form the bis-hydrido complex 8. Finally, these Ru-CNC's are active in catalytic hydrogenation of CO₂ to formate salts, and unlike the phosphine-containing Ru-PNP counterpart, they also catalyze the selective hydrogenation of esters to alcohols.