期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 139, 期 13, 页码 4948-4953出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b01441
关键词
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资金
- Fonds der Chemischen Industrie (Dozentenstipendium)
- European Research Council (ERC)
- Deutsche Forschungsgemeinschaft [AL 1348/5-1]
- Chinese Scholarship Council
- DAAD
A series Of new P boolean AND P-chelating ligands constituted by a dicationic [P(H(2)Im)(2)](+2) unit (H(2)Im = 1,3-clitnethy1-4,5-dihydroimidazol-2-ylidene) and a PPh2 group connected through structurally different backbones have been synthesized. Evaluation -of their reactivity toward different metal centers provides evidence that the dicationic fragment, otherwise reluctant to coordinate metals, readily participates in the formation of chelates when embedded into such a scaffold, Moreover, it significantly enhances the Lewis acidity of the metals to which it coordinates. This property has been used to develop a Rh catalyst that efficiently triggers the hydroarylation of dienes with electron -rich aromatic molecules. Kinetic studies and deuterium -labeling experiments, as well as density functional theory calculations,. were performed in order to rationalize these findings.
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