期刊
CHEMPLUSCHEM
卷 82, 期 2, 页码 212-224出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cplu.201600526
关键词
density functional calculations; hydrogenation; metalation; reaction mechanisms; ruthenium
资金
- German research foundation DFG within the transregional collaborative research center [SFB/TRR 88]
- state research center OPTIMAS
- research college MAGNENZ
- state research unit NanoKat
The synthesis of 2-substituted pyridine-pyrimidine ligands and their complexation with arene ruthenium(II) chloride moieties is reported. Depending on the electronic and steric influences of the ligand, the catalysts undergo CH activation by roll-over cyclometalation. This process opens up the route to the catalytic transfer hydrogenation of ketones with isopropanol as the hydrogen source under base-free and mild conditions. Barriers related to the roll-over cyclometalation process can be determined experimentally by collision-induced dissociation ESI mass spectrometry. They are supported by DFT calculations and allow the classification of the ligands according to their electronic and steric properties, which is also in accordance with critical bond parameters derived from X-ray structure data. DFT calculations furthermore reveal that the formation of a ruthenium(II) hydrido species is plausible through beta-hydride elimination from isopropanol.
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