Lutidine-derived Ru-CNC hydrogenation pincer catalysts with versatile coordination properties
Georgy A. Filonenko (Eindhoven University of Technology)
Elena Cosimi (DSM)
Laurent Lefort (DSM)
Matthew P. Conley (ETH Zürich)
Christophe Copéret (ETH Zürich)
Martin Lutz (Universiteit Utrecht)
Emiel J.M. Hensen (Eindhoven University of Technology)
Evgeny A. Pidko (Eindhoven University of Technology)
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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.
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