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

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journal contribution
posted on 10.08.2017, 15:34 by Zheng Wang, Xiangyang Chen, Bo Liu, Qing-Bin Liu, Gregory A. Solan, Xinzheng Yang, Wen-Hua Sun
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.

History

Citation

Catalysis Science and Technology, 2017, 7, 1297-1304

Author affiliation

/Organisation/COLLEGE OF SCIENCE AND ENGINEERING/Department of Chemistry

Version

AM (Accepted Manuscript)

Published in

Catalysis Science and Technology

Publisher

Royal Society of Chemistry

issn

2044-4753

eissn

2044-4761

Acceptance date

01/02/2017

Copyright date

2017

Available date

02/02/2018

Publisher version

http://pubs.rsc.org/en/Content/ArticleLanding/2017/CY/C6CY02413K#!divAbstract

Notes

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.

Language

en