Sung, Simon and Boon, Jie Kang and Lee, Johnathan J.C. and Rajabi, Nasir A. and Macgregor, Stuart A. and Krämer, Tobias and Young, Rowan D.
(2017)
Convergent (De)Hydrogenative Pathways via a Rhodium α-Hydroxylalkyl Complex.
Organometallics, 36 (8).
pp. 1609-1617.
ISSN 0276-7333
Abstract
We report the convergent reaction pathways between [RhH(PPh3)4] and POP ketone (1) and alcohol (2) ligands that terminate in the formation of an α-hydroxylalkyl rhodium(I) complex (3), representing two halves of a formal reduction/oxidation pathway between 1 and 2. In the case of hydride transfer to 1, the formation of the α-hydroxylalkyl rhodium(I) complex (3) proceeds via a rare hydrido(η2-carbonyl) complex (4). C–H activation in 2 at the proligand’s central methine position, rather than O–H activation of the hydroxy motif, followed by loss of dihydrogen also generates the α-hydroxylalkyl rhodium(I) complex (3). The validity of the postulated reaction pathways is probed with DFT calculations. The observed reactivity supports α-hydroxylalkyl complexes as competent intermediates in ketone hydrogenation catalyzed by rhodium hydrides and suggest that ligands 1 and 2 may be “noninnocent” coligands in reported hydrogenation catalyst systems in which they are utilized.
| Item Type: |
Article
|
| Keywords: |
Homogeneous Hydrogenation; Synthesis GAS; Carbon Monoxide;
Metallacyclic Manganese; Hydroxyalkyl Complexes; Ruthenium Complexes; Chemistry, Organic; Mechanistic Insight;
Noncovalent Interactions; Tropsch Type Reactions;
Reductive Elimination; Chemistry, inorganic & nuclear; |
| Academic Unit: |
Faculty of Science and Engineering > Chemistry |
| Item ID: |
11593 |
| Identification Number: |
https://doi.org/10.1021/acs.organomet.7b00158 |
| Depositing User: |
Tobias Kraemer
|
| Date Deposited: |
04 Nov 2019 15:00 |
| Journal or Publication Title: |
Organometallics |
| Publisher: |
American Chemical Society |
| Refereed: |
Yes |
| URI: |
|
| Use Licence: |
This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available
here |
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