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Unusual Rearrangement of Modified PNP Ligand based Ru Complexes Relevant to Alcohol Dehydrogenation Catalysis

preprint
submitted on 21.05.2019 and posted on 21.05.2019 by Shubham Deolka, Naziha Tarannam, Robert Fayzullin, sebastian kozuch, Eugene Khaskin
We report the synthesis of ‘hangman-type’ PNP pincer ligands and their associated Ru complexes. Upon deprotonation, the complexes undergo sp2-sp3 C-C bond cleavage and subsequent C-C formation processes to form a new, one carbon unit longer backbone motif. Unlike the starting geometry, the products are completely inactive in alcohol dehydrogenation catalysis. DFT and mechanistic studies suggest an intramolecular isomerization process via a spyrocycle cyclopropane intermediate, dependent upon arm pyridine coordination and ligand sterics.

History

Email Address of Submitting Author

eugenekhaskin@oist.jp

Institution

Okinawa Institute of Science and Technology

Country

Japan

ORCID For Submitting Author

0000-0003-1790-704X

Declaration of Conflict of Interest

No conflict of interest

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