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

preprint
submitted on 21.05.2019, 03:16 and posted on 21.05.2019, 15:57 by Shubham Deolka, Naziha Tarannam, Robert R. 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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