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The file associated with this record is under embargo until 12 months after publication, in accordance with the publisher's self-archiving policy. The full text may be available through the publisher links provided above.A catalyst loading of between 0.001–0.05 mol% of the PNN-bearing ruthenium(II) complex [fac-PNN]RuH(PPh3)(CO) (PNN = 8-(2-diphenylphosphinoethyl)amidotrihydroquinoline), in combination with 5 mol% NaBH4, efficiently catalyzes the hydrogenation of esters to their corresponding alcohols under mild pressures of hydrogen. Both aromatic and aliphatic esters can be converted with high values of TON or TOF achievable. Mechanistic investigations using both DFT calculations and labeling experiments highlight the cooperative role of NaBH4 in the catalysis while the catalytically active species has been established as trans-dihydride [mer-PNHN]RuH2(CO) (PNHN = 8-(2-diphenylphosphinoethyl)aminotrihydroquinoline). The stereo-structure of the PNHN-ruthenium species greatly affects the activity of the catalyst, and indeed the cis-dihydride isomer [fac-PNHN]RuH2(CO) is unable to catalyze the hydrogenation of esters until ligand reorganization occurs to give the trans isomer.Peer-reviewedPost-prin

catalysis science and technology

Cooperative interplay between a flexible PNN-Ru(<scp>ii</scp>) complex and a NaBH<sub>4</sub> additive in the efficient catalytic hydrogenation of esters

Cooperative interplay between a flexible PNN-Ru(ii) complex and a NaBH4 additive in the efficient catalytic hydrogenation of esters

Cooperative interplay between a flexible PNN-Ru(ii) complex and a NaBH₄ additive in the efficient catalytic hydrogenation of esters