Transition metals are known to be the essential part in most of the catalysts, the heterogeneous and the homogenous catalysts; however, the ligands that attached to the metal centers can also alter the reactivity of the catalyst, and that is widely observed in nature. In our project, we are interested in the metal-ligand cooperation of a special type of ligand called the pincer ligand. Our focus is mainly on the tridentate Pincer Ligands with a pyridine backbone. Also, it contains a spacer that could be deprotonated and protonated during the aromatization and dearomatization process. Aromatization and dearomatization of the pincer ligand are responsible for the unique reactivity of the pincer complexes, especially in the hydrogenation and dehydrogenation reactions.
Recently, huge developments have been made in the dehydrogenative coupling of aniline and benzyl alcohol via manganese pincer complexes. The most recent papers on that subject have been done by Beller in 2016[1], Kempe 2018 [2], and Hultzsch 2019 [3]. However, rhenium complexes have not been studied enough even though it is in the same seventh row of the transition metal.
Therefore, the rhenium was studied as a possible alternative. Then, the synthesis of a well-defined PN3 rhenium complex was performed from the bipy-tBu ligand and the metal precursor Re(CO)5Cl. The ligand has a unique deformity as the phosphine sidearm is not attached to the metal center.
Further investigation of the aniline and benzyl alcohol dehydrogenative coupling via PN3 rhenium pincer complex has been done. An optimal reaction condition was achieved, and the substrate scope was further examined with various alcohols and amines, and the result shows good to moderate conversion with decent selectivity towards the imine. Except for the secondary alcohols.
Identifer | oai:union.ndltd.org:kaust.edu.sa/oai:repository.kaust.edu.sa:10754/662703 |
Date | 04 1900 |
Creators | Alobaid, Nasser A. |
Contributors | Lai, Zhiping, Physical Science and Engineering (PSE) Division, Huang, Kuo-Wei, Rueping, Magnus |
Source Sets | King Abdullah University of Science and Technology |
Language | English |
Detected Language | English |
Type | Thesis |
Rights | 2021-05-01, At the time of archiving, the student author of this thesis opted to temporarily restrict access to it. The full text of this thesis will become available to the public after the expiration of the embargo on 2021-05-01. |
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