Student Authors
Student Authors:
Bryn K. Werley '23
Xintong Hou '18
Evan P. Bertonazzi '20
Document Type
Article
Publication Date
10-5-2023
Department 1
Chemistry
Abstract
(Cyclopentadienone)iron carbonyl compounds are catalytically active in carbonyl/imine reductions, alcohol oxidations, and borrowing hydrogen reactions, but the effect of cyclopentadienone electronics on their activity is not well established. A series of (tetraarylcyclopentadienone)iron tricarbonyl compounds with varied electron densities on the cyclopentadienone were prepared, and their activities in transfer hydrogenations and dehydrogenations were explored. Additionally, mechanistic studies, including kinetic isotope effect experiments and modifications to substrate electronics, were undertaken to gain insights into catalyst resting states and turnover-limiting steps of these reactions. As the cyclopentadienone electron density increased, both the transfer hydrogenation and dehydrogenation rates increased. A catalytically relevant, trimethylamine-ligated iron compound was isolated and characterized and was observed in solution under both transfer hydrogenation and dehydrogenation conditions. Importantly, it was catalytically active in both reactions. Kinetic isotope effect data and initial rates in transfer hydrogenation reactions with 4′-substituted acetophenones provided evidence that hydrogen transfer from the catalyst to the carbonyl substrate occurred during the turnover-limiting step, and NMR spectroscopy supports the trimethylamine adduct as an off-cycle resting state and the (hydroxycyclopentadienyl)iron hydride as an on-cycle resting state. In transfer dehydrogenations of alcohols, the use of electronically modified benzylic alcohols provided evidence that the turnover-limiting step involves the transfer of hydrogen from the alcohol substrate to the catalyst. The trimethylamine-ligated compound was proposed as the primary catalyst resting state in dehydrogenations.
Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 License.
DOI
10.1021/acs.organomet.3c00284
Version
Version of Record
Recommended Citation
Werley, Bryn K., Xintong Hou, Evan P. Bertonazzi, Anthony Chianese, and Timothy W. Funk. “Substituent Effects and Mechanistic Insights on the Catalytic Activities of (Tetraarylcyclopentadienone)Iron Carbonyl Compounds in Transfer Hydrogenations and Dehydrogenations.” Organometallics 42, no. 21 (2023): 3053–65. https://doi.org/10.1021/acs.organomet.3c00284.