Authors (13): G. J. Sherborne, M. R. Chapman, A. J. Blacker, R. A. Bourne, T. W. Chamberlain, B. D. Crossley, S. J. Lucas, P. C. McGowan, M. A. Newton, T. E. O. Screen, P. B. J. Thompson, C. E. Willans, B. N. Nguyen
Themes: BAG DOI: 10.1021/ja512868a
Citations: 21
Pub type: article-journal
Pub year: 2015
Publisher: American Chemical Society (ACS)
Issue: 12
License: http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html
Publication date(s): 2015/04 (print) 2015/03/20 (online)
Pages: 4151-4157
Volume: 137 Issue: 12
Journal: Journal of the American Chemical Society
Link: https://pubs.acs.org/doi/pdf/10.1021/ja512868a
URL: http://dx.doi.org/10.1021/ja512868a
A highly robust immobilized [Cp*IrCl2]2 precatalyst on Wang resin for transfer hydrogenation, which can be recycled up to 30 times, was studied using a novel combination of X-ray absorption spectroscopy (XAS) at Ir L3-edge, Cl K-edge, and K K-edge. These culminate in in situ XAS experiments that link structural changes of the Ir complex with its catalytic activity and its deactivation. Mercury poisoning and “hot filtration” experiments ruled out leached Ir as the active catalyst. Spectroscopic evidence indicates the exchange of one chloride ligand with an alkoxide to generate the active precatalyst. The exchange of the second chloride ligand, however, leads to a potassium alkoxide–iridate species as the deactivated form of this immobilized catalyst. These findings could be widely applicable to the many homogeneous transfer hydrogenation catalysts with Cp*IrCl substructure.
| Name | Description | Publised |
|---|---|---|
| ja512868a_si_001.pdf | Supl. data for Activation and Deactivation of a Robust Immobilized Cp*Ir... | 2015 |
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